Cationic polymers and fixative application therefor

ABSTRACT

This invention relates to cationic  Cassia  polymers and to their use in hair fixative applications. The cationic  Cassia  polymers demonstrate superior stiffness profiles and a high level of curl retention when subjected to high humidity conditions for extended periods of time.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.11/843,920 filed on Aug. 23, 2007, now U.S. Pat. No. 7,439,214, which isa continuation of U.S. application Ser. No. 10/874,296, filed on Jun.18, 2004, now U.S. Pat. No. 7,262,157, which claims priority from U.S.Provisional Application Ser. No. 60/479,793, filed on Jun. 19, 2003.

TECHNICAL FIELD

This invention generally relates to polygalactomannan derivatives. Morespecifically, the invention relates to cationically functionalizedgalactomannan polymers obtained from Cassia tora and Cassia obtusifoliaand their use in personal care, health care, household, institutionaland industrial products and the like. The cationically functionalizedgalactomannan polymers can be employed as thickeners, stabilizers,emulsifiers, spreading aids, hair fixatives, and carriers for enhancingthe efficacy, deposition and delivery of chemically and physiologicallyactive ingredients. In addition, these polymers are useful for improvingthe psychosensory and aesthetic properties of cosmetic formulations inwhich they are included.

BACKGROUND

Polygalactomannans are polysaccharides that are found in the endospermmaterial of seeds from leguminous plants such as Cyamopsis tetragonoloba(guar gum), Cesalpinia spinosa (tara gum), Ceratonia siliqua (locustbean gum), and other members of the Leguminosae family. Apolygalactomannan is composed of backbone of 1→4-linkedβ-D-mannopyranosyl units with recurring 1→6-linked α-D-galactosyl sidegroups branching from the number 6 carbon of a mannopyranose residue inthe backbone. The galactomannan polymers of the different Leguminosaespecies defer from one another in the frequency of the occurrence of thegalactosyl side units branching from the polymannopyranose backbone. Theaverage ratio of D-mannosyl to D-galactosyl units in thepolygalactomannan contained in guar gum is approximately 2:1,approximately 3:1 for tara gum, and approximately 4:1 for locust beangum. Another important source of polygalactomannan is Cassia tora andCassia obtusifolia (collectively known as Cassia gum). The average ratioof D-mannosyl to D-galactosyl units in the polygalactomannan containedin Cassia gum is at least 5:1.

Polygalactomannan obtained from Cassia gum is schematically representedin the structure below:

wherein n is an integer representing the number of repeating units inthe polymer. The cationic polygalactomannan used in the practice of thisinvention typically has a weight average molecular weight (Mw) rangingfrom 200,000 to 3,000,000 Daltons in one aspect, 300,000 to 2,000,000Daltons in another aspect, and 400,000 to 1,000,000 Daltons in a furtheraspect of the invention.

Polygalactomannans are hydrocolloids that have a high affinity forwater. They have been widely used as suspending, thickening,emulsifying, and gelling agents in applications as diverse asfoodstuffs, coatings, personal care compositions and in oil wellfracturing fluids. Although the use of these polymers has been met withgreat success, polygalactomannans used in their natural form havesuffered some drawbacks from a water solubility standpoint. Anunsubstituted polymannose backbone is completely insoluble in water. Theattachment of galactose side units to the C-6 atom in the recurringmannose residues of the polymannose backbone increases the watersolubility of the polymer, particularly in cold water (i.e., ambienttemperature and below). The greater the galactose side unitsubstitution, the greater is the cold water solubility properties of thepolygalactomannan. Consequently, lower ratios of D-mannosyl toD-galactosyl units in the polygalactomannan leads to better cold watersolubility. For example, guar gum polygalactomannan (average D-mannosylto D-galactosyl ratio 2:1) is soluble in cold water; while Cassia gumpolygalactomannan (average D-mannosyl to D-galactosyl ratio of 5:1) isonly sparingly soluble in cold and hot water.

U.S. Pat. No. 4,753,659 to Bayerlein et al. discloses inter alia thatimproved cold water solubility can be imparted to Cassia gum bychemically modifying the polygalactomannan. Disclosed uses for thechemically modified Cassia gum polygalactomannans include textileprinting applications, oil well drilling mud auxiliaries, and mining andexplosive applications.

U.S. Pat. No. 5,733,854 to Chowdhary et al. discloses a chemicallymodified guar gum and a method for its preparation. According toChowdhary et al., cationically functionalized guar gumpolygalactomannans produce clear and colorless solutions upon dispersalin aqueous or organic solvents. A disclosed application for thecationically functionalized guar gum includes its incorporation intodetergent compositions for human and household uses. Other discloseduses include personal care and cosmetic applications. The use ofcationically functionalized Cassia gum in hair fixative formulations isnot discussed.

Accordingly, there exists is a need for a cationic polygalactomannanwith a high degree of cationic functionalization which is suitable foruse in thickener, stabilizer, emulsifier, spreading aid, hair fixativeand in carrier applications for enhancing the efficacy, deposition anddelivery of chemically, cosmetically and physiologically activeingredients.

The desire to have one's hair retain a particular set or coiffure iswidely held. A common methodology for accomplishing this is by applyinga “fixative” to the hair. Hair fixative compositions can assist inmanipulating (styling) the hair, and provide temporary benefits inholding the shape of the hair style (fixing) and maintaining the shineor appearance (grooming, restyling) of the coiffure during the day orbetween hair washing periods with water or shampoo, or betweensubsequent hair setting procedures.

The term “fixative” as applied to the cationic Cassia polymers of thepresent invention encompasses the properties of film-formation,adhesion, or coating deposited on a keratinous surface (e.g., hair andskin) on which the polymer is applied. The terms “hair styling and hairfixative” as commonly understood in the hair care art, and as usedherein, refer collectively to hair setting agents that are hairfixatives and film formers and which are topically applied to the hairto actively contribute to the ease of styling and/or holding of a hairset, and to maintain the restylability of the hair set. Hence, hairsetting compositions include hair styling, hair fixative, and hairgrooming products that conventionally are applied to the hair (wet ordry) in the form of gels, rinses, emulsions (oil-in-water, water-in-oilor multiphase), such as lotions and creams, pomades, sprays (pressurizedor non-pressurized), spritzes, foams, such as mousses, shampoos, solids,such as sticks, semisolids and the like, or are applied from a hairsetting aid having the hair setting composition impregnated therein orcoated thereon, to leave the hair setting agent in contact on the hairfor some period until removed, as by washing.

Various objective and subjective methods are used to measure theefficacy of a hair fixative composition. One method commonly employedevaluates the resistance of the hair set to high humidity conditions asa function of curl retention. When curl retention is measured undercontrolled ambient temperatures in the range of about 23° to about 27°C. and high humidity in the range of about 80 to 90% relative humidity(RH), it is commonly referred to as high humidity curl retention (HHCR).Most conventional hair fixative formulations are marginally effective,typically providing an HHCR of about 70% of the initial curl for aperiod of not more than about 0.75 hours. Thus there is an ongoing needfor an increase in the HHCR of hair fixative or hair settingformulations.

One of the most common needs in the hair fixative market today is stiffhair feel and stiff hold. This is especially desirable in men's styling,in products targeting younger consumers, and in regions where hair ismore tenacious and requires greater holding power such as Asia and LatinAmerica. Thus, the demand for stiff hold is a growing trend. Traditionalstiff-hold styling polymers have many deficiencies including poorhumidity resistance, tackiness or stickiness and excessive flaking.Accordingly, there is an ongoing need for an easy-to-use polymer thatprovides both superior stiffness and superior high humidity styleretention performance.

Also of importance are the aesthetic characteristics and appearance ofhair fixative or hair setting compositions before, during, and afterapplication to hair. In one aspect of the invention, the productviscosity should be non-runny to avoid dripping during application. Inanother aspect, product clarity is substantially transparent or clear inorder to obtain a “clean” product appearance. The product should be easyto spread, have a smooth texture, a non-tacky feel, and be able to dryrelatively quickly on the hair.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot comparing the percent of spiral curl retention underhigh humidity conditions of hair tresses treated with fixativecompositions containing cationic Cassia of the present inventioncompared to hair tresses treated with an identically formulated fixativecomposition containing commercially available cationic guar.

FIG. 2 is a plot of the percent high humidity curl retention vs. timeobtained from fixative gel samples containing a blend of 2 wt. %cationic Cassia of the invention and 1 wt. % guar gum.

FIG. 3 is a plot of the Peak Force (Newtons) needed to deflect fixativetreated hair swatches centered across the span of two support legs of a3-point bending rig.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Exemplary embodiments in accordance with the present invention will bedescribed. Various modifications, adaptations or variations of suchexemplary embodiments described herein may become apparent to thoseskilled in the art as such are disclosed. It will be understood that allsuch modifications, adaptations or variations that rely upon theteachings of the present invention, and through which these teachingshave advanced the art, are considered to be within the scope and spiritof the present invention.

One aspect of the present invention relates to the use of a cationicallyfunctionalized Cassia galactomannan polymer (Cassia polygalactomannan)as a fixative polymer having superior curl retention and stiffnessproperties. In one hair setting aspect, the efficacy of the hairfixative is evaluated herein by its ability to provide high humiditycurl resistance or retention (HHCR) to the hair. HHCR refers to theresistance of a hair set to relaxation (i.e., reversion to its originalconfiguration) or loss of curl when exposed to a high humidity in therange of about 90% relative humidity, measured in terms of % curlretention (CR) over selected time intervals as described in more detailherein.

In another hair setting aspect, the efficacy of the hair fixative isevaluated herein by its ability to provide high mechanical stiffnessproperties. Mechanical stiffness refers to the Peak Force, in Newtons,required to bend a fixative treated hair tress mounted on a three-pointbending rig as described in more detail herein.

The cationic Cassia polymers of this invention can be employed as thesole fixative component in a hair fixative composition or can beformulated in combination with one or more hydrocolloid polymers, one ormore rheology modifiers, one or more auxiliary fixative polymers, one ormore adjuvants and additives, commonly employed in hair fixativecompositions; and combinations thereof. Such hydrocolloid polymers,rheology modifiers, auxiliary fixative polymers, adjuvants and additivesare described hereinbelow.

The cationic Cassia polymers of this invention can be formulated toobtain fixative products in the form of gels, rinses, emulsions(oil-in-water, water-in-oil or multiphase), such as lotions and creams,pomades, waxes, sprays, (pressurized or non-pressurized), spritzes,foams, such as mousses, shampoos, solids, such as sticks, semisolids andthe like.

In one aspect of the invention, hair fixative formulations containingthe cationic Cassia polymers can be delivered from water, water/organicsolvent mixtures, or solvent/propellant systems. In another aspect, thecationic Cassia polymers are dissolved in a polar solvent, such as wateror water-alcohol mixture.

The hair fixative compositions of the invention can be provided anddispensed from assorted package forms known in the art, i.e.,pressurized and non-pressurized containers, such as cans, bottles,packets, ampoules, jars, tubes, and the like. In another packaged formembodiment, the hair fixative composition can be dispensed to the hairfrom a hair setting aid impregnated with the hair fixative compositionor coated with the hair setting composition. The term “hair settingaid”, as used herein, refers to wipes, pads, towlettes, sponges, curlingpapers, hair combs, hair brushes, hair curlers, such as sponge hairrollers, and the like, that can serve as substrates for holding anddelivering cationic Cassia polymer to hair. The hair setting aid can beimpregnated with hair fixative composition, such as by soaking,immersing, saturating, and the like, or the hair setting aid can becoated with the hair fixative composition, such as by brushing,spraying, dipping, and the like, and then packaged, while wet or insubstantially dried form.

Hair fixative spray compositions can be dispensed from finger-actuatedpump devices, either as pressurized aerosol sprays, mousses, spritzes,and foams containing propellant, or as non-pressurized, mechanicallypropelled sprays and foams. When a cationic Cassia polymer of theinvention is formulated into a pressurized aerosol composition, thepropellant can be any conventional hydrocarbon such as, for example,fluorinated hydrocarbons, selected from difluoroethane,tetrafluoroethane, hexafluoroethane, and mixtures thereof; dimethylether; liquid volatile hydrocarbons, such as, for example, propane,isobutene, n-butane and mixtures thereof; and compressed gas, such as,for example, carbon dioxide, nitrous oxide and nitrogen. The amount ofpropellant is governed by the spray characteristic and pressure factorsdesired as is well known in the aerosol art. In one aspect, pressurizedaerosol hair fixative compositions contain concentrations ofenvironmentally and physiologically acceptable solvent/propellantcombinations that meet legislated federal and state governmentalrequirements for volatile organic compounds (VOC). For low VOCcompositions, the solvent system in one aspect is water based. Inanother aspect, the solvent system can include at least about 20 wt. %to about 50 wt. % water. In another aspect, the solvent system containsnot more than about 25 wt. % of organic solvent. For mousse products,the level of propellant can be in the range of about 1 wt. % to about 30wt. % in one aspect, and from about 3 wt. % to about 15 wt. % in anotheraspect, based on the total weight of the fixative composition.

Foam hair fixative compositions can be of a “post-foaming” gel to amousse type product where volatile liquid hydrocarbon is dispersed inthe hair fixative composition and then packaged in a container, such as,for example, a bag-in-can, SEPRO-can, sealed and pressurized on theoutside of the bag, as known in the art. Alternatively, foam hairfixative compositions can be a gel or mousse formulation that ismechanically aerosolized by placing it in a finger-actuatednon-pressurized pump dispenser.

The hair fixative compositions of the invention can be formulated ashair cosmetic type products containing hair colorants, such as colorantstyling gels or styling sticks for concurrently providing temporary haircolor.

In one aspect, the present invention relates to Cassiapolygalactomannans that are cationically functionalized to attainvarying degrees of cationic group content which can be expressed ascationic charge density (hereafter referred to a charge density). Inother aspects the present invention relates to cationicallyfunctionalized Cassia gum polygalactomannan that is tailored for use asa thickener, stabilizer, emulsifier, spreading aid, fixative, andcarriers for enhancing the efficacy, deposition and delivery ofchemically and physiologically active ingredients.

As used here and throughout the specification, the term “cationicallyfunctionalized” refers to a polymer that has been modified to contain acationic group containing moiety. In the present invention, a cationicgroup containing moiety is reacted with a hydroxyl group(s) on themannosyl and/or galactosyl units that comprise the Cassiapolygalactomannan polymer. In the reaction the hydroxyl hydrogen isreplaced by a moiety derived from the cationic functionalizationreagent. In one embodiment, the hydroxyl hydrogen on the C-6 carbon atomis replaced by a moiety derived from the cationic functionalizationreagent. The reaction is schematically represented below:

In some embodiments of the invention, R independently representshydrogen or a cationic group, subject to the proviso that all R groupscan not be hydrogen at the same time. In other embodiments, Rindependently is selected from the formula:-AR¹wherein A is an alkylene spacer group containing 1 to 6 carbon atoms andR¹ represents a cationic substituent. In another embodiment the alkylenegroup contains 2, 3, 4, or 5 carbon atoms. The alkylene spacer isoptionally mono-substituted or multi-substituted with a group selectedfrom C₁ to C₃ alkyl, C₁ to C₃ haloalkyl, C₁ to C₃ hydroxyalkyl,hydroxyl, halogen (bromine, chlorine, fluorine, and iodine), andcombinations thereof; and n represents the number of repeating unitsnecessary to attain a weight average molecular weight (Mw) ranging from200,000 to 3,000,000 Daltons in one aspect, 300,000 to 2,000,000 Daltonsin another aspect, and 400,000 to 1,000,000 Daltons in a further aspectof the invention.

Exemplary cationic substituents under R¹ includes cationic ammonium,sulfonium and phosphonium moieties represented by the radicals: —N(R³)₃⁺X⁻, —S(R³)₂ ⁺X⁻, —P(R³)₃ ⁺X⁻, wherein R³ independently represents C₁ toC₂₄ alkyl, benzyl and phenyl; and X is any suitable anion that balancesthe charge on the onium cation. In one embodiment, X is a halide anionselected from bromine, chlorine, fluorine and iodine. The alkyl, benzyland phenyl substituents defined under R³ can optionally bemono-substituted or multi-substituted with a group selected from C₁ toC₃ alkyl, hydroxyl, halogen (bromine, chlorine, fluorine, and iodine),and combinations thereof. Illustrative cationic groups defined under-AR¹ can be represented by the formulae:-alkylene-N(R³)₃ ⁺X⁻-alkylene-S(R³)₂ ⁺X⁻-alkylene-P(R³)₃ ⁺X⁻wherein alkylene, R², R³, and X are as previously defined.Representative of cationic groups under -AR¹ are quaternary ammoniumgroups that include but are not limited to the formula:

wherein R³ is selected from C₁ to C₂₄ alkyl, benzyl and phenyl in oneaspect and methyl, decyl, dodecyl, butadecyl, cocoalkyl, dodecyl, andoctadecyl in another aspect, and R⁴ is selected from hydrogen andchlorine. In another aspect the quaternary ammonium group is2-hydroxy-3-(trimethylammonium)propyl chloride represented by theformula:

Underivatized Cassia gum or flour is commercially available fromLubrizol Advanced Materials, Inc., Noveon® Consumer SpecialtiesDivision, under the Novegum™ trademark. In one aspect of the presentinvention the charge density of the cationically functionalized Cassiaranges from about 0.1 meq/g to about 7 meq/g, from about 0.5 meq/g toabout 4 meq/g in another aspect, and from about 0.6 meq/g to about 3meq/g in still another aspect. The charge density of a cationic polymerof the invention can be calculated as follows:

${{CD}\left( {{meq}\text{/}g} \right)} = {\frac{{{Wt}.\mspace{11mu}\%}\mspace{14mu}{{of}\begin{pmatrix}{{Nitrogen},{Sulfur},} \\{{or}\mspace{14mu}{Phosphorus}}\end{pmatrix}}\mspace{14mu}{in}\mspace{14mu}{the}\mspace{14mu}{polymer}}{{{Molecular}\mspace{14mu}{{Wt}.\;{{of}\begin{pmatrix}{{Nitrogen},{Sulfur},} \\{{or}\mspace{14mu}{Phosphorus}}\end{pmatrix}}}\; \times 100}\mspace{11mu}} \times 1000}$

The functionalization of the Cassia polygalactomannan hydroxyl group(s)can be accomplished by methods well known to those skilled in the art.Generally speaking, a hydroxyl group on the Cassia polymer backbone canbe reacted with any functionalization reagent containing a cationicmoiety that is reactive therewith. For example, to cationicallyfunctionalize Cassia gum, a hydroxyl group(s) on the Cassia gumpolygalactomannan is reacted with a functionalization reagent thatcontains a cationic substituent and a functional moiety that is reactivewith a hydroxyl group. The functionalization reaction is conducted in anappropriate solvent and at an appropriate temperature. The amount offunctional group substitution (i.e., charge density) can be controlledby adjusting the stoichiometric amount of the functionalization reagentadded to the Cassia polygalactomannan. Functionalization methods forCassia gum polygalactomannans are disclosed in U.S. Pat. No. 4,753,659which is incorporated herein by reference. Additional methods offunctionalizing polygalactomannans are set forth in U.S. Pat. No.5,733,854.

While not intending to be bound by theory, it is surmised that the C-6hydroxyl groups on the polygalactomannan are more reactive tofunctionalization than the C-2 and C-3 hydroxyl groups on the mannosyland galactosyl units and the C-4 hydroxyl group on the galactosyl unitsdue to steric considerations. Notwithstanding the foregoing, it iscontemplated that any free hydroxyl group(s) on the polygalactomannanbackbone can be functionalized with the cationic functionalizationreagent. In this embodiment the cationically functionalized repeatingunit can be represented as follows:

wherein R represents hydrogen or a cationic group, subject to theproviso that all R groups can not be hydrogen at the same time, and Rand n are as previously defined.

In an exemplary reaction, Cassia gum polygalactomannan can becationically functionalized with co-reactive quaternary ammoniumcompounds that contain a reactive epoxy group or a halohydrin group. Inone such embodiment Cassia gum can reacted withglycidyltrimethylammonium chloride (75% aqueous solution) in an alkalineaqueous medium at a temperature of about 52° C. to yield the desired2-hydroxy-3-(trimethylammonium)propyl Cassia galactomannan chlorideproduct. The reaction is schematically represented below:

In the schematic representation above, the C-6 hydroxyl groups on thepolymer are shown to be fully functionalized in this embodiment. Inother embodiments of the invention, some but not all of the C-6 hydroxylgroups can be cationically functionalized. In still other embodiments,one or more of the C-2 and/or one or more of the C-3 hydroxyl groups onthe mannosyl and galactosyl units and/or one or more of the C-4 hydroxylgroups on the galactosyl units of the polymer can be cationicallyfunctionalized.

Chemical modification of Cassia gum leads to incorporation of thecationic moiety, onto the backbone. The chemical modification leads tovarious physical property changes. For instance, cationic Cassiapolymers exhibit cold water or improved cold water solubility. It isable to hydrate in cold water and build viscosity by forming a colloidalthixotopic dispersion in cold water.

In a given composition or application, the cationic Cassia polymers ofthis invention can, but need not, serve more than one function, such asa fixative, thickener, skin and hair conditioner, film former andcarrier or deposition aid. In a fixative composition the amount ofcationic Cassia polymer that can be employed depends upon the purposefor which they are included in the formulation and can be determined byperson skilled in the hair fixative formulation art. Thus, as long asthe desired physicochemical and functional properties are achieved, auseful amount of cationic Cassia polymer on a total composition weightbasis, typically can vary in the range of from about 0.01% to about 25%in one aspect of the invention, from about 0.1 wt. % to about 10 wt. %in another aspect, and from about 0.2 wt. % to about 5 wt. % in afurther aspect of the invention, based on the total weight of thecomposition, but is not limited thereto.

In addition to its fixative properties, the cationic Cassia polymers ofthe invention can be employed as conditioners and/or deposition aids inhair fixative and styling shampoo compositions. The cationic Cassiapolymer can be used in shampoos and conditioners to facilitatecombability. The positively charged nitrogen atom interacts with thenegatively charged hair fibers to form films. They also make the hairfeel softer and smoother to the touch without creating excessiveresidual build-up. Cationic Cassia polymers can be used as part of aconditioner package in a conditioning detergent formulation that notonly imparts cleansing, wet detangling, dry detangling and manageabilityproperties to the hair, but also is relatively non-irritating. Thiscomposition is thus suitable for use by young children and adults havingsensitive skin and eyes. In addition, cationic Cassia has been found tobe an excellent deposition aid in the deposition of conditioning andtherapeutic agents to the hair.

In styling shampoo, the use of the cationic Cassia polymers of thepresent invention as deposition aids to enhance the deposition ofwater-insoluble styling polymers improves the styling performance(conditioning, curl retention, superior hair feel) of the hair. Thecationic Cassia polymers of the invention can be used as deposition aidsin combination with water-insoluble hair styling polymers selected fromthe group of (meth)acrylates copolymers and silicone-grafted(meth)acrylates. Examples include t-butylacrylate/2-ethylhexylacrylatecopolymers, t-butylacrylate/2-ethylhexylmethacrylate copolymers, t-butylacrylate/2-ethylhexyl methacrylate/polydimethylsiloxane macromer, andt-butyl methacrylate/2-ethylhexylmethacrylate/polydimethylsiloxanemacromer copolymers, and mixtures thereof.

Hair fixative product formulations comprising the cationic Cassiapolymers of the invention can contain various additives and cosmeticadjuvants, conventionally or popularly included in hair fixativecompositions, as are well known in the art. In one embodiment of theinvention the cationic Cassia fixative polymers of the invention can beformulated in combination with derivatized and non-derivatizedhydrocolloids derived from natural sources such as, for example,polysaccharides obtained from tree, shrub, and fruit exudates, such asgum arabic, gum gahatti, and gum tragacanth, and pectin; seaweedextracts, such as alginates and carrageenans; algae extracts, such asagar; microorganism produced polysaccharides, such as xanthan, gellan,and wellan gums; cellulose ethers, such as ethylhexylethylcellulose(EHEC), hydroxybutylmethylcellulose (HBMC), hydroxyethylmethylcellulose(HEMC), hydroxypropylmethylcellulose (HPMC), methyl cellulose (MC),carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC),hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose;polygalactomannan gums selected from fenugreek, Cassia, locust bean,tara and guar; and mixtures thereof.

By derivatized hydrocolloid is meant that the above mentionedhydrocolloids can be derivatized with a functionalization agent reactivewith a functional group, e.g., a hydroxyl group, contained on thehydrocolloid backbone. For example, derivatives of the cellulose etherscontaining quaternary ammonium groups can be made by reacting acellulose ether, e.g., hydroxyethylcellulose, with an epoxidesubstituted by a trialkyl ammonium salt group, e.g.,glycidyltrimethylammonium chloride, to give the quaternary substitutedcellulose.

Derivatized hydrocolloids can be made by grafting a cellulose ether suchas hydroxymethylcellulose, hydroxyethylcellulose orhydroxypropylcellulose with a free radically polymerizable,ethylenically unsaturated quaternary ammonium salts such asN,N,N-trimethylaminoethyl methacrylate methyl sulfate or halide,2-hydroxy-3-methacryloxypropyl trimethyl ammonium methyl sulfate orhalide, vinyl benzyl trialkyl ammonium methyl sulfate or halide, dialkyldiallyl ammonium methyl sulfate or halide; sodium or ammonium styrenesulfonate. Such polymers are described in U.S. Pat. No. 4,131,576.

Derivatized hydrocolloids can also be made by quaternizing apolygalactomannan such as locust bean gum or guar with a quaternizingagent. Quaternized polygalactomannans can be made by reacting guar gumwith a haloalkyl substituted quaternary ammonium compound, e.g.,4-chloro-2-butenyl trimethylammonium chloride. A process for producingderivatized polygalactomannan gums is described in U.S. Pat. No.4,031,307.

When the above mentioned hydrocolloids are formulated into the fixativecomposition of the present invention the weight ratio of cationic Cassiafixative to hydrocolloid(s) range from about 1:10 to about 10:1 in oneaspect, from about 2:8 to about 8:2 in another aspect, from about2.5:7.5 to about 7.5:2.5 in a further aspect, from about 1:5 to about5:1 in another aspect, and from about 1:2 to about 2:1 in a stillfurther aspect.

Surprisingly, it was discovered that the blends of cationic Cassia andnon-derivatized guar gum provide an unexpected synergy in rheology andfixative properties. Mechanical blends of cationic Cassia and guarachieve superior viscosity and yield values when compared to the sum ofthe individual viscosity and yield values for cationic Cassia and guar.The same effect was noted for curl retention and hair stiffness values.An optimum synergistic effect for rheology and fixative properties wasnoted at cationic Cassia to guar weight ratios of from about 1:1 toabout 2:1.

For the individual galactomannan hydrocolloids optimum fixativeproperties can be achieved if the ratio of cationic Cassia polymers ofthe invention to the above described polysaccharides on a wt. to wt.basis is between about 9:1 and about 1:9 in one aspect, between about8:2 and 2:8 in another aspect, between about 6:4 and 4:6 in a furtheraspect, between about 2:1 to 1:2 is still further aspect, and 1:1 inanother aspect.

In another embodiment of the invention the cationic Cassia fixativepolymers of the invention can be formulated in combination with one ormore auxiliary rheology modifiers. Suitable rheology modifiers includesynthetic and semi-synthetic rheology modifiers. Exemplary syntheticrheology modifiers include acrylic based polymers and copolymers. Oneclass of acrylic based rheology modifiers are the carboxyl functionalalkali-swellable and alkali-soluble thickeners (ASTs) produced by thefree-radical polymerization of acrylic acid alone or in combination withother ethylenically unsaturated monomers. The polymers can besynthesized by solvent/precipitation as well as emulsion polymerizationtechniques. Exemplary synthetic rheology modifiers of this class includehomopolymers of acrylic acid or methacrylic acid and copolymerspolymerized from one or more monomers of acrylic acid, substitutedacrylic acid, and salts and C₁-C₃₀ alkyl esters of acrylic acid andsubstituted acrylic acid. As defined herein, the substituted acrylicacid contains a substituent positioned on the alpha and/or beta carbonatom of the molecule wherein the substituent is preferably andindependently selected from C₁₋₄ alkyl, —CN, and —COOH. Optionally,other ethylenically unsaturated monomers such as, for example, styrene,vinyl acetate, ethylene, butadiene, acrylonitrile, as well as mixturesthereof can be copolymerized into the backbone. The foregoing polymersare optionally crosslinked by a monomer that contains two or moremoieties that contain ethylenic unsaturation. In one aspect, thecrosslinker is selected from a polyalkenyl polyether of a polyhydricalcohol containing at least two alkenyl ether groups per molecule. OtherExemplary crosslinkers are selected from allyl ethers of sucrose andallyl ethers of pentaerythritol, and mixtures thereof. These polymersare more fully described in U.S. Pat. No. 5,087,445; U.S. Pat. No.4,509,949; and U.S. Pat. No. 2,798,053 herein incorporated by reference.

In one embodiment the AST rheology modifier is a crosslinked homopolymerpolymerized from acrylic acid or methacrylic acid and is generallyreferred to under the INCI name of Carbomer. Commercially availableCarbomers include Carbopol® polymers 934, 940, 941, 956, 980 and 996available from Lubrizol Advanced Materials, Inc. In another embodimentthe AST rheology modifier is selected from a crosslinked copolymerpolymerized from a first monomer selected from one or more monomers of(meth)acrylic acid, substituted acrylic acid, and salts of (meth)acrylicacid and substituted acrylic acid and a second monomer selected from oneor more C₁-C₅ alkyl acrylate esters of (meth)acrylic acid. Thesepolymers are designated under the INCI name of Acrylates Copolymer.Acrylates Copolymers are commercially available under the trade namesAculyn® 33 from Rohm and Haas and Carbopol® Aqua SF-1 from LubrizolAdvanced Materials, Inc. In a further aspect the rheology modifier isselected from a crosslinked copolymer polymerized from a first monomerselected from one or more monomers of acrylic acid, substituted acrylicacid, salts of acrylic acid and salts of substituted acrylic acid and asecond monomer selected from one or more C₁₀-C₃₀ alkyl acrylate estersof acrylic acid or methacrylic acid. In one aspect the monomers can bepolymerized in the presence of a steric stabilizer such as disclosed inU.S. Pat. No. 5,288,814 which is herein incorporated by reference. Someof the forgoing polymers are designated under INCI nomenclature asAcrylates/C10-30 Alkyl Acrylate Crosspolymer and are commerciallyavailable under the trade names Carbopol® 1342 and 1382, Carbopol®Ultrez 20 and 21, Carbopol® ETD 2020 and Pemulen® TR-1 and TR-2 fromLubrizol Advanced Materials, Inc. Any vinyl or acrylic based rheologymodifiers are suitable.

Another class of synthetic rheology modifiers suitable for use in thepresent invention includes hydrophobically modified ASTs commonlyreferred to as hydrophobically modified alkali-swellable andalkali-soluble emulsion (HASE) polymers. Typical HASE polymers are freeradical addition polymers polymerized from pH sensitive or hydrophilicmonomers (e.g., acrylic acid and/or methacrylic acid), hydrophobicmonomers (e.g., C₁-C₃₀ alkyl esters of acrylic acid and/or methacrylicacid, acrylonitrile, styrene), an “associative monomer”, and an optionalcrosslinking monomer. The associative monomer comprises an ethylenicallyunsaturated polymerizable end group, a non-ionic hydrophilic midsectionthat is terminated by a hydrophobic end group. The non-ionic hydrophilicmidsection comprises a polyoxyalkylene group, e.g., polyethylene oxide,polypropylene oxide, or mixtures of polyethylene oxide/polypropyleneoxide segments. The terminal hydrophobic end group is typically a C₈-C₄₀aliphatic moiety. Exemplary aliphatic moieties are selected from linearand branched alkyl substituents, linear and branched alkenylsubstituents, carbocyclic substituents, aryl substituents, aralkylsubstituents, arylalkyl substituents, and alkylaryl substituents. In oneaspect associative monomers can be prepared by the condensation (e.g.,esterification or etherification) of a polyethoxylated and/orpolypropoxylated aliphatic alcohol (typically containing a branched orunbranched C₈-C₄₀ aliphatic moiety) with an ethylenically unsaturatedmonomer containing a carboxylic acid group (e.g., acrylic acid,methacrylic acid), an unsaturated cyclic anhydride monomer (e.g., maleicanhydride, itaconic anhydride, citraconic anhydride), amonoethylenically unsaturated monoisocyanate (e.g.,α,α-dimethyl-m-isopropenyl benzyl isocyanate) or an ethylenicallyunsaturated monomer containing a hydroxyl group (e.g., vinyl alcohol,allyl alcohol). Polyethoxylated and/or polypropoxylated aliphaticalcohols are ethylene oxide and/or propylene oxide adducts of amonoalcohol containing the C₈-C₄₀ aliphatic moiety. Non-limitingexamples of alcohols containing a C₈-C₄₀ aliphatic moiety are caprylalcohol, iso-octyl alcohol (2-ethyl hexanol), pelargonic alcohol(1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetylalcohol, cetyl alcohol, cetearyl alcohol (mixture of C₁₆-C₁₈monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol,oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol,ceryl alcohol, montanyl alcohol, melissyl, lacceryl alcohol, geddylalcohol, and C₂-C₂₀ alkyl substituted phenols (e.g., nonyl phenol), andthe like.

Exemplary HASE polymers are disclosed in U.S. Pat. Nos. 3,657,175;4,384,096; 4,464,524; 4,801,671; and 5,292,843 which are hereinincorporated by reference. In addition, an extensive review of HASEpolymers is found in Gregory D. Shay, Chapter 25, “Alkali-Swellable andAlkali-Soluble Thickener Technology A Review”, Polymers in AqueousMedia—Performance Through Association, Advances in Chemistry Series 223,J. Edward Glass (ed.), ACS, pp. 457-494, Division Polymeric Materials,Washington, D.C. (1989), the relevant disclosures of which areincorporated herein by reference. The HASE polymers are commerciallyavailable from Rohm & Haas under the trade designations Aculyn® 22 (INCIName: Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 44 (INCIName: PEG-150/Decyl Alcohol/SMDI Copolymer), Aculyn 46® (INCI Name:PEG-150/Stearyl Alcohol/SMDI Copolymer), and Aculyn® 88 (INCI Name:Acrylates/Steareth-20 Methacrylate Crosspolymer).

Another class of synthetic and semi-synthetic rheology modifierssuitable for use in the present invention includes cationically modifiedacrylic polymers and copolymers and cationically modified celluloseethers. The acrylic polymers and copolymers and cellulose ethers arecationically modified via quaternization. For the acrylic polymers andcopolymers, quaternization can occur by polymerizing a quaternizedmonomer into the acrylic polymer backbone or by post functionalizing theacrylic polymer with a quaternizing agent. An exemplary quaternaryacrylic polymer is designated under INCI nomenclature asPolyquaternium-37 and is commercially available under the trade namesSynthalen CR21 and Synthalen CN, from 3V Inc. The quaternized cellulosesare prepared by post functionalizing the desired cellulosic backbone(e.g., hydroxyethyl cellulose) with a quaternizing agent such as aquaternary ammonium salt (e.g, diallyldimethyl ammonium chloride,trimethyl ammonium chloride substituted epoxide). Exemplary quaternarycellulosic polymers are designated under the INCI namesPolyquaternium-4, Polyquaternium-10, and Polyquaternium-67.

In another embodiment, acid swellable associative polymers can be usedwith the cationic fixatives of the present invention. Such polymersgenerally have cationic and associative characteristics. These polymersare free radical addition polymers polymerized from a monomer mixturecomprising an acid sensitive amino substituted hydrophilic monomer(e.g., dialkylamino alkyl (meth)acrylates or (meth)acrylamides), anassociative monomer (defined hereinabove), a lower alkyl(meth)acrylateor other free radically polymerizable comonomers selected fromhydroxyalkyl esters of (meth)acrylic acid, vinyl and/or allyl ethers ofpolyethylene glycol, vinyl and/or allyl ethers of polypropylene glycol,vinyl and/or allyl ethers of polyethylene glycol/polypropylene glycol,polyethylene glycol esters of (meth)acrylic acid, polypropylene glycolesters of (meth)acrylic acid, polyethylene glycol/polypropylene glycolesters of (meth)acrylic acid), and combinations thereof. These polymerscan optionally be crosslinked. By acid sensitive is meant that the aminosubstituent becomes cationic at low pH values, typically ranging fromabout 0.5 to about 6.5. Exemplary acid swellable associative polymersare commercially available under the trade name Structure® Plus (INCIName: Acrylates/Aminoacrylates/C10-C30 Alkyl PEG-20 Itaconate) fromNational Starch and Chemical Company, and Carbopol® Aqua CC (INCI Name:Polyacrylates-1 Crosspolymer) from Lubrizol Advanced Materials, Inc. Inone aspect the acid swellable polymer is a copolymer of one or moreC₁-C₅ alkyl esters of (meth)acrylic acid, C₁-C₄ dialkylamino C₁-C₆ alkylmethacrylate, PEG/PPG-30/5 alkyl ether, PEG 20-25 C₁₀-C₃₀ alkyl ethermethacrylate, hydroxy C₂-C₆ alkyl methacrylate crosslinked with ethyleneglycol dimethacrylate. Other useful acid swellable associative polymersare disclosed in U.S. Pat. No. 7,378,479, the disclosure of which isherein incorporated by reference.

Hydrophobically modified alkoxylated methyl glucoside, such as, forexample, PEG-120 Methyl Glucose Dioleate, PEG-120 Methyl GlucoseTrioleate, and PEG-20 Methyl Glucose Sesquistearate, available fromLubrizol Advanced Materials, Inc., under the trade names, Glucamate®DOE-120, Glucamate™ LT, and Glucamate™ SSE-20, respectively, are alsosuitable rheology modifiers.

Other rheology modifiers suitable for use in the fixative compositionsof the invention are disclosed in U.S. Pat. No. 7,205,271 the disclosureof which is herein incorporated by reference.

The rheology modifiers set forth above, when employed, can be used aloneor in combination and typically are used in an amount ranging from about0.1 wt. % to about 5 wt. % in one aspect, from about 0.3 wt. % to about3 wt. % in another aspect, and from about 0.5 wt. % to about 2 wt. % infurther aspect, based on the total weight of the fixative compositionsof the present invention.

In another embodiment of the invention the cationic Cassia fixativepolymers of the invention can be formulated in combination with anauxiliary fixative(s). Suitable optional auxiliary hair fixativepolymers include natural and synthetic polymers such as, for example,polyacrylates, polyvinyls, polyesters, polyurethanes, polyamides,modified cellulose, starches, and mixtures thereof. These polymers canbe nonionic, anionic, cationic and amphoteric in nature and includewithout limitation one or more of polyoxythylenated vinylacetate/crotonic acid copolymers, vinyl acetate crotonic acidcopolymers, vinyl methacrylate copolymers, monoalkyl esters ofpoly(methyl vinyl ether (PVM)/maleic acid (MA)), such as, for example,ethyl, butyl and isopropyl esters of PVM/MA copolymer acrylic acid/ethylacrylate/N-tert-butyl-acrylamide terpolymers, and poly(methacrylicacid/acrylamidomethyl propane sulfonic acid), acrylates copolymer,octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,acrylates/octylacrylamide copolymer, vinyl acetate (VA)/crotonates/vinylneodeanoate copolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide),corn starch modified, sodium polystyrene sulfonate, polyquaterniums suchas, for example, Polyquaternium-4, Polyquaternium-11, Polyquaternium-24,Polyquaternium-28, Polyquaternium-29, Polyquaternium-32,Polyquaternium-34, Polyquaternium-37, Polyquaternium-39,Polyquaternium-44, Polyquaternium-46, Polyquaternium-47,Polyquarternium-55, Polyquaternium-69, Polyquaternium-87, polyether-1,polyurethanes, VA/acrylates/lauryl methacrylate copolymer, adipicacid/dimethylaminohydroxypropyl diethylene AMP/acrylates copolymer,methacrylol ethyl betaine/acrylates copolymer, polyvinylpyrrolidone(PVP), vinyl pyrrolidone (VP)/dimethylaminoethylmethacrylate copolymer,VP/methacrylamide/vinyl imidazole copolymer, VP/dimethylaminopropylamine(DMAPA) acrylates copolymer, VP/vinylcaprolactam/DMAPA acrylatescopolymer, VP/dimethylaminoethylmethacrylate copolymer, VP/DMAPAacrylates copolymer, vinyl caprolactam/VP/dimethylaminoethylmethacrylate copolymer, VA/butyl maleate/isobornyl acrylate copolymer,VA/crotonates copolymer, acrylate/acrylamide copolymer,VA/crotonates/vinyl propionate copolymer, VP/vinyl acetate/vinylpropionate terpolymers, VA/crotonates, VP/vinyl acetate copolymer,VP/acrylates copolymer, VA/crotonic acid/vinyl proprionate,acrylates/acrylamide, acrylates/octylacrylamide,acrylates/hydroxyacrylates copolymer, acrylates/hydroxyesteracrylatescopolymer, acrylates/stereth-20 methacrylate copolymer, tert-butylacrylate/acrylic acid copolymer,diglycol/cyclohexanedimethanol/isophthalates/sulfoisophthalatescopolymer, VA/butyl maleate and isobornyl acrylate copolymer,vinylcaprolactam/VP/dimethylaminoethyl methacrylate, VA/alkylmaleatehalf ester/N-substituted acrylamide terpolymers, vinylcaprolactam/VP/methacryloamidopropyl trimethylammonium chlorideterpolymer, methacrylates/acrylates copolymer/amine salt,polyvinylcaprolactam, polyurethanes, hydroxypropyl guar,poly(methacrylic acid/acrylamidomethyl propane sulfonic acid (AMPSA),ethylenecarboxamide (EC)/AMPSA/methacrylic acid (MAA),poylurethane/acrylate copolymers and hydroxypropyl trimmonium chlorideguar, acrylates copolymer, acrylates crosspolymer, AMP-acrylates/allylmethacrylate copolymer, polyacrylate-14, polyacrylate-2 crosspolymer,octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,acrylates/octylacrylamide copolymer, VA/crotonates/vinyl neodeanoatecopolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide),polyurethane, acrylates/lauryl acrylate/stearyl acrylate/ethylamineoxide methacrylate copolymer, methacryloyl ethyl betaines/methacrylatescopolymer, corn starch modified, sodium polystyrene sulfonate,polyurethane/acrylates copolymer, pyrrolidone carboxylic acid salt ofchitosan, chitosan glycolate, cationic polygalactomannans, such as, forexample, quaternized derivatives of guar, such as, for example, guarhydroxypropyl trimmonium chloride and hydroxypropyl guar hydroxypropyltrimmonium chloride. Many of the foregoing polymers are referred to bytheir INCI nomenclature set forth in the International CosmeticIngredient Dictionary published by the Cosmetic, Toiletry, and FragranceAssociation, Washington D.C. Other suitable auxiliary fixative polymersare disclosed in U.S. Pat. No. 7,205,271, the disclosure of which isherein incorporated by reference.

The fixative polymer, alone or in combination with the optionalauxiliary fixative(s), typically comprises about 0.01 wt. % to about 25wt. % in one aspect, from about 0.1 wt. % to about 10 wt. % in anotheraspect, and about 0.2 wt. % to about 5 wt. % in a further aspect of thetotal weight of the fixative composition. The optional fixative polymercan be present in the amount of from 0 wt. % to about 24.99 wt. % of thetotal fixative composition.

One or more cosmetically acceptable adjuvants and additives can beincluded in the hair fixative compositions of the invention. Suchadjuvants and additives include but are not limited to pH adjustingagents or buffering agents, emulsifiers, emollients, surfactants,conditioning agents, and mixtures thereof.

The pH adjusting agent is utilized in any amount necessary to obtain adesired pH value in the fixative composition. In one aspect, thefixative composition of the invention can contain at least onealkalizing (alkaline pH adjusting agent) or acidifying agent (acidic pHadjusting agent) in amounts from 0.01 to 30 wt. % of the total weight ofthe composition. Non-limiting examples of alkaline pH adjusting agentsinclude ammonia, alkali metal hydroxides, such as sodium hydroxide, andpotassium hydroxide; ammonium hydroxide, alkanolamines such as mono-,di- and triethanolamine; diisopropylamine, dodecylamine,diisopropanolamine, aminomethyl propanol, cocamine, oleamine,morpholine, triamylamine, triethylamine, tromethamine(2-amino-2-hydroxymethyl)-1,3-propanediol), andtetrakis(hydroxypropyl)ethylenediamine; and alkali metal salts ofinorganic acids, such as sodium borate (borax), sodium phosphate, sodiumpyrophosphate, and the like, and mixtures thereof. Non-limiting examplesof acidic pH adjusting agents include organic acids, such as citricacid, acetic acid, alpha-hydroxy acid, beta-hydroxy acid, salicylicacid, lactic acid, glycolic acid, natural fruit acids, and combinationsthereof. In addition, inorganic acids, for example hydrochloric acid,nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, andcombinations thereof can be utilized.

The emulsifier can be selected from a water-in-oil emulsifier, anoil-in-water emulsifier, and mixtures thereof. In one aspect of theinvention the emulsifier can be present in an amount ranging from about0.5 wt. % to about 12 wt. %, from about 1 wt. % to about 15 wt. % inanother aspect, and from about 5 wt. % to about 10 wt. % in a furtheraspect, based on the total weight of the fixative composition.

Exemplary emulsifiers include but are not limited to C₁₂-C₁₈ fattyalcohols; alkoxylated C₁₂-C₁₈ fatty alcohols; C₁₂-C₁₈ fatty acids; andalkoxylated C₁₂-C₁₈ fatty acids, the alkoxylates each having 10 to 30units of ethylene oxide, propylene oxide, and combinations of ethyleneoxide/propylene oxide; C₈-C₂₂ alkyl mono- and oligoglycosides;ethoxylated sterols; partial esters of polyglycerols; esters and partialesters of polyols having 2 to 6 carbon atoms and saturated andunsaturated fatty acids having 12 to 30 carbon atoms; partial esters ofpolyglycerols; and organosiloxanes; and combinations thereof.

The fatty alcohols, acids and alkoxylated fatty alcohols and fatty acidsare as described in the emollient description above. In one aspect ofthe invention the fatty alcohols and fatty acids each are ethoxylatedwith 10 to 30 units of ethylene oxide.

The C₈-C₂₂ alkyl mono- and oligoglycoside emulsifiers are prepared byreacting glucose or an oligosaccharide with primary fatty alcoholshaving 8 to 22 carbon atoms. Products which are obtainable under thetrademark Plantacare® comprise a glucosidically bonded C₈-C₁₆ alkylgroup on an oligoglucoside residue whose average degree ofoligomerization is 1 to 2. Exemplary alkyl glucosides andoligoglycosides are selected from octyl glucoside, decyl glucoside,lauryl glucoside, palmityl glucoside, isostearyl glucoside, stearylglucoside, arachidyl glucoside and behenyl glucoside, and mixturesthereof.

Exemplary ethoxylated sterols include ethoxylated vegetable oil sterolssuch as, for example, soya sterols. The degree of ethoxylation isgreater than about 5 in one aspect, and at least about 10 in anotheraspect. Suitable ethoxylated sterols are PEG-10 Soy Sterol, PEG-16 SoySterol and PEG-25 Soy Sterol.

The partial esters of polyglycerols have 2 to 10 glycerol units and areesterified with 1 to 4 saturated or unsaturated, linear or branched,optionally hydroxylated C₈-C₃₀ fatty acid residues. Representativepartial esters of polyglycerols include diglycerol monocaprylate,diglycerol monocaprate, diglycerol monolaurate, triglycerolmonocaprylate, triglycerol monocaprate, triglycerol monolaurate,tetraglycerol monocaprylate, tetraglycerol monocaprate, tetraglycerolmonolaurate, pentaglycerol monocaprylate, pentaglycerol monocaprate,pentaglycerol monolaurate, hexaglycerol monocaprylate, hexaglycerolmonocaprate, hexaglycerol monolaurate, hexaglycerol monomyristate,hexaglycerol monostearate, decaglycerol monocaprylate, decaglycerolmonocaprate, decaglycerol monolaurate, decaglycerol monomyristate,decaglycerol monoisostearate, decaglycerol monostearate, decaglycerolmonooleate, decaglycerol monohydroxystearate, decaglycerol dicaprylate,decaglycerol dicaprate, decaglycerol dilaurate, decaglyceroldimyristate, decaglycerol diisostearate, decaglycerol distearate,decaglycerol dioleate, decaglycerol dihydroxystearate, decaglyceroltricaprylate, decaglycerol tricaprate, decaglycerol trilaurate,decaglycerol trimyristate, decaglycerol triisostearate, decaglyceroltristearate, decaglycerol trioleate, decaglycerol trihydroxystearate,and mixtures thereof.

The saturated C₁₂-C₃₀ fatty alcohol emulsifiers are as described in theemollient description set forth above. In one aspect of the invention,the fatty alcohol emulsifier is selected from but not limited to cetylalcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolinalcohol or mixtures of these alcohols, and as are obtainable in thehydrogenation of unsaturated vegetable oil and animal fatty acids.

Emulsifiers based on the esters and partial esters of polyols having 2to 6 carbon atoms and linear saturated and unsaturated fatty acidshaving 12 to 30 carbon atoms are, for example, the monoesters anddiesters of glycerol or ethylene glycol or the monoesters of propyleneglycol with saturated and unsaturated C₁₂ to C₃₀ fatty acids.

The partially esterified polyglycerol emulsifiers include 2 to about 10glycerol units and esterified with 1 to 5 saturated or unsaturated,linear or branched, optionally hydroxylated C₈ to C₃₀ fatty acidresidues.

The organosiloxane emulsifiers are polymeric emulsifiers that contain atleast one hydrophobic portion and at least one hydrophilic portion. Thepolymer backbone contains repeating siloxy units that can have cyclic,linear or branched repeating units, e.g. di(C₁-C₅)alkylsiloxy units,typically dimethylsiloxy units.

The hydrophilic portion of the organosiloxane is generally achieved bysubstitution onto the polymeric backbone of a residue that confershydrophilic properties to a portion of the molecule. The hydrophilicresidue may be substituted on a terminus of the polymericorganosiloxane, or on any one or more repeating units of the polymer.Generally, the hydrophilic residue is derived from ethylene oxide unitsthat are grafted onto the polymer backbone. In general, the repeatingdimethylsiloxy units of modified polydimethylsiloxane emulsifiers arehydrophobic in nature due to the methyl groups, and confer thehydrophobicity properties to the molecule. In addition, longer chainalkyl residues, hydroxy terminated polypropyleneoxy residues, hydroxyterminated polyether residues comprising a combination of ethyeleneoxide and propylene oxide residues, and/or other types of residues canbe substituted onto the siloxy backbone to confer additionalemulsification properties to the backbone. Polyether substitutedorganosiloxane emulsifiers are known as dimethicone copolyols and arewidely commercially available. The dimethicone polyols can be random orblock copolymers. A generally useful class of dimethicone polyols isblock copolymers having blocks of polydimethylsiloxane and blocks ofpolyalkylene oxide, such as blocks of polyethylene oxide, polypropyleneoxide, or both.

Dimethicone copolyols are disclosed in U.S. Pat. Nos. 5,136,063 and5,180,843, the disclosures of which are incorporated herein byreference. In addition, dimethicone copolyols are commercially availableunder the Silsoft® and Silwet® brand names from the General ElectricCompany (GE-OSi). Specific product designations include but are notlimited to Silsoft 305, 430, 475, 810, 895, Silwet L 7604 (GE-OSi); DowCorning® 5103 and 5329 from Dow Corning Corporation; and Abil®dimethicone copolyols, such as, for example WE 09, WS 08, EM 90 and EM97 from Degussa Goldschmidt Corporation; and Silsense™ dimethiconecopolyols, such as Silsense Copolyol-1 and Silsense Copolyol-7,available from Lubrizol Advanced Materials, Inc.

Blends of dimethicone copolyols in cyclomethicone fluids are also usefulemulsifiers in the present invention. An exemplarydimethicone/cyclomethicone blend is commercially available as DowCorning® 5225 C and is a 10 wt. % dispersion of PEG/PPG-18/18Dimethicone in cyclopentasiloxane fluid available from Dow CorningCorporation.

Suitable emollients include but are not limited to an emollient selectedfrom silicone fluids (e.g., volatile silicone oils and non-volatilesilicone oils); mineral oils; petrolatums; vegetable oils; fish oils;fatty alcohols; fatty acids; fatty acid and fatty alcohol esters;alkoxylated fatty alcohols; alkoxylated fatty acid esters; benzoateesters; Guerbet esters; alkyl ether derivatives of polyethylene glycols,such as, for example methoxypolyethylene glycol (MPEG); and polyalkyleneglycols; lanolin and lanolin derivatives; and the like. The emollientcan be used alone or in combination with one or more emollients of thepresent invention. The emollient(s) can be utilized in an amount rangingfrom about 0.5 wt. % to about 30 wt. % by weight of the total fixativecomposition in one aspect 0.1 wt. % to 25 wt. % in another aspect, and 5wt. % to 20 wt. % in a further aspect.

Volatile silicone oils include cyclic and linear polydimethylsiloxanes,low molecular weight organo-functional silicones, and the like. Cyclicvolatile silicones (cyclomethicones) typically contain about 3 to about7 silicon atoms, alternating with oxygen atoms, in a cyclic ringstructure. Each silicon atom is typically substituted with two alkylgroups, such as, for example, methyl groups. Volatile linearpolydimethylsiloxanes (dimethicones) typically contain about 2 to about9 silicon atoms, alternating with oxygen atoms in a linear arrangement.Each silicon atom is also substituted with two alkyl groups (theterminal silicon atoms are substituted with three alkyl groups), suchas, for example, methyl groups. The linear volatile silicones typicallyhave viscosities of less than about 5 cP at 25° C., while the cyclicvolatile silicones typically have viscosities of less than about 10 cPat 25° C. “Volatile” means that the silicone has a measurable vaporpressure, or a vapor pressure of at least 2 mm of Hg at 20° C.Non-volatile silicones have a vapor pressure of less than 2 mm Hg at 20°C. A description of volatile silicones is found in Todd and Byers,“Volatile Silicone Fluids for Cosmetics”, Cosmetics and Toiletries, Vol.91(1), pp. 27-32 (1976), and in Kasprzak, “Volatile Silicones”,Soap/Cosmetics/Chemical Specialties, pp. 40-43 (December 1986), eachincorporated herein by reference.

Exemplary volatile cyclomethicones are D4 cyclomethicone(octamethylcyclotetrasiloxane), D5 cyclomethicone(decamethylcyclopentasiloxane), D6 cyclomethicone, and blends thereof(e.g., D4/D5 and D5/D6). Volatile cyclomethicones and cyclomethiconeblends are commercially available from G.E. Silicones as SF1173, SF1202,SF1256, and SF1258, Dow Corning Corporation as Dow Corning® 244, 245,246, 345, and 1401 Fluids. Blends of volatile cyclomethicones andvolatile linear dimethicones are also contemplated.

Exemplary volatile linear dimethicones include hexamethyldisiloxane,octamethyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane and blends thereof. Volatile lineardimethicones and dimethicone blends are commercially available from DowCorning Corporation as Dow Corning 200® Fluid (e.g., productdesignations 0.65 CST, 1 CST, 1.5 CST, and 2 CST) and Dow Corning®2-1184 Fluid.

Exemplary volatile low molecular weight organo-functional siliconesinclude phenyl trimethicone, caprylyl trimethicone, caprylyl methicone,and hexyl methicone, and blends thereof. Low molecular weightorgano-functional silicones are commercially available from Clariantunder the trade name Silcare® 41M10, Slicare® 31M60, Silcare® 41M10, andSilcare® 41M15.

The non-volatile silicone oils useful as emollients in the presentinvention are linear and typically have viscosities of from about 10 cPto about 100,000 cP at 25° C. They typically contain above about 10dialkyl/diaryl or monoalkyl/monoaryl substituted silicon atoms,alternating with oxygen atoms in a linear arrangement. They includepolyalkylsiloxane, polyarylsiloxane, and polyalkylarylsiloxane polymers.Exemplary non-volatile silicone oils include the polydimethylsiloxanes(dimethicones), polydiethylsiloxanes, polymethylphenylsiloxanes, and thelike. In one aspect of the invention, the non-volatile silicone oil isselected from a non-volatile polydimethylsiloxane having a viscosityrange from about 10 cP to about 100,000 cP at 25° C. Non-volatiledimethicones are commercially available from Dow Corning Corporation asDow Corning 200® Fluid (product designations 10 CST through 10,000 CST).

Mineral oils and petrolatums include cosmetic, USP and NF grades and arecommercially available from Penreco under the Drakeol® and Penreco®trade names. Mineral oil includes hexadecane and paraffin oil.

Exemplary vegetable oils suitable an emollient component in the presentinvention include but are not limited to peanut oil, sesame oil, avocadooil, coconut oil, cocoa butter, almond oil, safflower oil, corn oil,cotton seed oil, sesame seed oil, walnut oil, castor oil, olive oil,jojoba oil, palm oil, palm kernel oil, soybean oil, wheat germ oil,linseed oil, sunflower seed oil; and the mono-, di-, and triglyceridesthereof. Exemplary mono-, di- and triglycerides are, for example,caprylic triglyceride, capric triglyceride, caprylic/caprictriglyceride, and caprylic/capric/lauric triglyceride,caprylic/capric/stearic triglyceride, and caprylic/capric/linoleictriglyceride.

Ethoxylated mono- and diglycerides are also suitable as an emollientcomponent of the present invention, such as, for example, PEG-8Caprylic/Capric Glycerides.

Suitable fatty alcohol emollients include but are not limited to fattyalcohols containing 8 to 30 carbon atoms. Exemplary fatty alcoholsinclude capryl alcohol, pelargonic alcohol, capric alcohol, laurylalcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearylalchohol, isostearyl alcohol, cetearyl alcohol, oleyl alcohol,ricinoleyl alcohol, arachidyl alcohol, icocenyl alcohol, behenylalcohol, and mixtures thereof.

Suitable fatty acid emollients include but are not limited to fattyacids containing 10 to 30 carbon atoms. Exemplary fatty acids areselected from capric acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid,and mixtures thereof.

Suitable fatty acid and fatty alcohol ester emollients include but arenot limited to hexyl laurate, decyl oleate, isopropyl stearate,isopropyl isostearate, butyl stearate, octyl stearate, cetyl stearate,myristyl myristate, octyldodecyl stearoylstearate, octylhydroxystearate,diisopropyl adipate, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, isodecyl oleate, isodecyl neopentanoate, diisopropylsebacate, isostearyl lactate, lauryl lactate, diethyl hexyl maleate,PPG-14 butyl ether and PPG-2 myristyl ether propionate, cetearyloctanoate, and mixtures thereof.

Alkoxylated fatty alcohols are ethers formed from the reaction of afatty alcohol with an alkylene oxide, generally ethylene oxide orpropylene oxide. Suitable ethoxylated fatty alcohols are adducts offatty alcohols and polyethylene oxide. In one aspect of the invention,the ethoxylated fatty alcohols can be represented by the formulaR—(OCH₂CH₂)_(n)—OH, wherein R represents the aliphatic residue of theparent fatty alcohol and n represents the number of molecules ofethylene oxide. In another aspect of the invention, R is derived from afatty alcohol containing 8 to 30 carbon atoms. In one aspect, n is aninteger ranging from 2 to 50, 3 to 25 in another aspect, and 3 to 10 ina further aspect. In a still further aspect, R is derived from a fattyalcohol emollient set forth above. Exemplary ethoxylated fatty alcoholsare but are not limited to capryl alcohol ethoxylate, lauryl alcoholethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate,stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate oleyl alcoholethoxylate, and, behenyl alcohol ethoxylate, wherein the number ofethylene oxide units in each of the foregoing ethoxylates can range from2 and above in one aspect, and from 2 to about 150 in another aspect. Itis to be recognized that the propoxylated adducts of the foregoing fattyalcohols and mixed ethoxylated/propoxylated adducts of the foregoingfatty alcohols are also contemplated within the scope of the invention.The ethylene oxide and propylene oxide units of theethoxylated/propoxylated fatty alcohols can be arranged in random or inblocky order.

More specific examples of ethoxylated alcohols are but are not limitedto Beheneth 5-30 (the 5-30 meaning the range of repeating ethylene oxideunits), Ceteareth 2-100, Ceteth 1-45, Cetoleth 24-25, Choleth 10-24,Coceth 3-10, C9-11 pareth 3-8, C11-15 pareth 5-40, C11-21 Pareth 3-10,C12-13 pareth 3-15, Deceth 4-6, Dodoxynol 5-12, Glycereth 7-26,Isoceteth 10-30, Isodeceth 4-6, Isolaureth 3-6, isosteareth 3-50, Laneth5-75, Laureth 1-40, Nonoxynol 1-120, Nonylnonoxynol 5-150, Octoxynol3-70, Oleth 2-50, PEG 4-350, Steareth 2-100, and Trideceth 2-10.

Specific examples of propoxylated alcohols are but are not limited toPPG-10 Cetyl Ether, PPG-20 Cetyl Ether, PPG-28 Cetyl Ether, PPG-30 CetylEther, PPG-50 Cetyl Ether, PPG-2 Lanolin Alcohol Ether, PPG-5 LanolinAlcohol Ether, PPG-10 Lanolin Alcohol Ether, PPG-20 Lanolin AlcoholEther, PPG-30 Lanolin Alcohol Ether, PPG-4 Lauryl Ether, PPG-7 LaurylEther, PPG-10 Oleyl Ether, PPG-20 Oleyl Ether, PPG-23 Oleyl Ether,PPG-30 Oleyl Ether, PPG-37 Oleyl Ether, PPG-50 Oleyl Ether, PPG-11Stearyl Ether, PPG-15 Stearyl Ether, PPG-2 Lanolin Ether, PPG-5 LanolinEther, PPG-10 Lanolin Ether, PPG-20 Lanolin Ether, PPG-30 Lanolin Ether,and PPG-1 Myristyl Ether.

Specific examples of ethoxylated/propoxylated alcohols are but are notlimited to PPG-1 Beheneth-15, PPG-12 Capryleth-18, PPG-2-Ceteareth-9,PPG-4-Ceteareth-12, PPG-10-Ceteareth-20, PPG-1-Ceteth-1, PPG-1-Ceteth-5,PPG-1-Ceteth-10, PPG-1-Ceteth-20, PPG-2-Ceteth-1, PPG-2-Ceteth-5,PPG-2-Ceteth-10, PPG-2-Ceteth-20, PPG-4-Ceteth-1, PPG-4-Ceteth-5,PPG-4-Ceteth-10, PPG-4-Ceteth-20, PPG-5-Ceteth-20, PPG-8-Ceteth-1,PPG-8-Ceteth-2, PPG-8-Ceteth-5, PPG-8-Ceteth-10, PPG-8-Ceteth-20, PPG-2C12-13 Pareth-8, PPG-2 C12-15 Pareth-6, PPG-4 C13-15 Pareth-15, PPG-5C9-15 Pareth-6, PPG-6 C9-11 Pareth-5, PPG-6 C12-15 Pareth-12, PPG-6C12-18 Pareth-11, PPG-3 C12-14 Sec-Pareth-7, PPG-4 C12-14 Sec-Pareth-5,PPG-5 C12-14 Sec-Pareth-7, PPG-5 C12-14 Sec-Pareth-9, PPG-1-Deceth-6,PPG-2-Deceth-3, PPG-2-Deceth-5, PPG-2-Deceth-7, PPG-2-Deceth-10,PPG-2-Deceth-12, PPG-2-Deceth-15, PPG-2-Deceth-20, PPG-2-Deceth-30,PPG-2-Deceth-40, PPG-2-Deceth-50, PPG-2-Deceth-60, PPG-4-Deceth-4,PPG-4-Deceth-6, PPG-6-Deceth-4, PPG-6-Deceth-9, PPG-8-Deceth-6,PPG-14-Deceth-6, PPG-6-Decyltetradeceth-12, PPG-6-Decyltetradeceth-20,PPG-6-Decyltetradeceth-30, PPG-13-Decyltetradeceth-24,PPG-20-Decyltetradeceth-10, PPG-2-Isodeceth-4, PPG-2-Isodeceth-6,PPG-2-Isodeceth-8, PPG-2-Isodeceth-9, PPG-2-Isodeceth-10,PPG-2-Isodeceth-12, PPG-2-Isodeceth-18, PPG-2-Isodeceth-25,PPG-4-Isodeceth-10, PPG-12-Laneth-50, PPG-2-Laureth-5, PPG-2-Laureth-8,PPG-2-Laureth-12, PPG-3-Laureth-8, PPG-3-Laureth-9, PPG-3-Laureth-10,PPG-3-Laureth-12, PPG-4 Laureth-2, PPG-4 Laureth-5, PPG-4 Laureth-7,PPG-4-Laureth-15, PPG-5-Laureth-5, PPG-6-Laureth-3, PPG-25-Laureth-25,PPG-7 Lauryl Ether, PPG-3-Myreth-3, PPG-3-Myreth-11, PPG-20-PEG-20Hydrogenated Lanolin, PPG-2-PEG-11 Hydrogenated Lauryl Alcohol Ether,PPG-12-PEG-50 Lanolin, PPG-12-PEG-65 Lanolin Oil, PPG-40-PEG-60 LanolinOil, PPG-1-PEG-9 Lauryl Glycol Ether, PPG-3-PEG-6 Oleyl Ether,PPG-23-Steareth-34, PPG-30 Steareth-4, PPG-34-Steareth-3, PPG-38Steareth-6, PPG-1 Trideceth-6, PPG-4 Trideceth-6, and PPG-6 Trideceth-8.

Alkoxylated fatty acids are formed when a fatty acid is reacted with analkylene oxide or with a pre-formed polymeric ether. The resultingproduct may be a monoester, diester, or mixture thereof. Suitableethoxylated fatty acid ester emollients suitable for use in the presentinvention are products of the addition of ethylene oxide to fatty acids.The product is a polyethylene oxide ester of a fatty acid. In one aspectof the invention, the ethoxylated fatty acid esters can be representedby the formula R—C(O)O(CH₂CH₂O)_(n)—H, wherein R represents thealiphatic residue of a fatty acid and n represents the number ofmolecules of ethylene oxide. In another aspect, n is an integer rangingfrom 2 to 50, 3 to 25 in another aspect, and 3 to 10 in a furtheraspect. In still another aspect of the invention, R is derived from afatty acid containing 8 to 24 carbon atoms. In a still further aspect, Ris derived from a fatty acid emollient set forth above. It is to berecognized that propoxylated and ethoxylated/propoxylated products ofthe foregoing fatty acids are also contemplated within the scope of theinvention. Exemplary alkoxylated fatty acid esters include but are notlimited to capric acid ethoxylate, lauric acid ethoxylate, myristic acidethoxylate, stearic acid ethoxylate, oleic acid ethoxylate, coconutfatty acid ethoxylate, and polyethylene glycol 400 propoxylatedmonolaurate, wherein the number of ethylene oxide units in each of theforegoing ethoxylates can range from 2 and above in one aspect, and from2 to about 50 in another aspect. More specific examples of ethoxylatedfatty acids are PEG-8 distearate (the 8 meaning the number of repeatingethylene oxide units), PEG-8 behenate, PEG-8 caprate, PEG-8 caprylate,PEG-8 caprylate/caprate, PEG cocoates (PEG without a number designationmeaning that the number of ethylene oxide units ranges from 2 to 50),PEG-15 dicocoate, PEG-2 diisononanoate, PEG-8 diisostearate,PEG-dilaurates, PEG-dioleates PEG-distearates, PEG Ditallates,PEG-isostearates, PEG-jojoba acids, PEG-laurates, PEG-linolenates,PEG-myristates, PEG-oleates, PEG-palmitates, PEG-ricinoleates,PEG-stearates, PEG-tallates, and the like.

Guerbet ester emollients are formed from the esterification reaction ofa Guerbet alcohol with a carboxylic acid. Guerbet ester emollients arecommercially available from the Noveon Consumer Specialties Division ofLubrizol Advanced Materials, Inc. under product designations G-20, G-36,G-38, and G-66.

Lanolin and lanolin derivatives are selected from lanolin, lanolin wax,lanolin oil, lanolin alcohols, lanolin fatty acids, alkoxylated lanolin,isopropyl lanolate, acetylated lanolin alcohols, and combinationsthereof. Lanolin and lanolin derivatives are commercially available fromthe Noveon Consumer Specialties Division of Lubrizol Advance Materials,Inc. under the trade names Lanolin LP 108 USP, Lanolin USP AAA,Acetulan™, Ceralan™, Lanocerin™, Lanogel™ (product designations 21 and41), Lanogene™, Modulan™, Ohlan™, Solulan™ (product designations 16, 75,L-575, 98, and C-24), Vilvanolin™ (product designations C, CAB, L-101,and P).

Surfactants are generally employed as cleansing agents, emulsifyingagents, stabilizers, foam boosters, structurants, hydrotropes andsuspending agents. While amounts of the surfactant if employed can varywidely, the amounts which are often utilized generally range from about1 wt. % to about 80 wt. % of the in one aspect, from about 5 wt. % toabout 65 wt. % in another aspect, from about 6 wt. % to about 30 wt. %in a further aspect, and from about 8 wt. % to about 20 wt. % in a stillfurther aspect of the invention, based upon the total weight of thefixative composition. The surfactant can be selected from any class ofsurfactants, i.e., anionic surfactants, cationic surfactants, nonionicsurfactants, amphoteric surfactants, and mixtures thereof. The term“amphoteric surfactant” as used herein includes zwitterionicsurfactants. In-depth discussions of the various classes of surfactantsare contained in the Cosmetics & Toiletries® C&T Ingredient ResourceSeries, “Surfactant Encyclopedia”, 2nd Edition, Rieger (ed), AlluredPublishing Corporation (1996); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, published 1949; and Surface ActiveAgents and Detergents, Volume II, published 1958, IntersciencePublishers; each incorporated herein by reference.

Anionic surfactants include substances having a negatively chargedhydrophobe or that carry a negative charge when the pH is elevated toneutrality or above, such as acylamino acids, and salts thereof, forexample, acylglutamates, acyl peptides, sarcosinates, and taurates;carboxylic acids, and salts thereof, for example, alkanolic acids andalkanoates, ester carboxylic acids, and ether carboxylic acids;phosphoric acid ester and salts thereof; sulfonic acids and saltsthereof, for example, acyl isethionates, alkylaryl sulfonates, alkylsulfonates, and sulfosuccinates; and sulfuric acid esters, such as alkylether sulfates and alkyl sulfates.

Non-limiting examples of anionic surfactants include mono-basic salts ofacylglutamates that are slightly acidic in aqueous solution, such assodium acylglutamate and sodium hydrogenated tallow glutamate; salts ofacyl-hydrolyzed protein, such as potassium, palmitoyl hydrolyzed milkprotein, sodium cocoyl hydrolyzed soy protein, and TEA-abietoylhydrolyzed collagen; salts of acyl sarcosinates, such as ammoniummyristoyl sarcosine, sodium cocoyl sarcosinate, and TEA-lauroylsarcosinate; salts of sodium methyl acyltaurates, such as sodium lauroyltaurate, sodium methyl oleyl taurate and sodium methyl cocoyl taurate;alkanoic acids and alkanoates, such as fatty acids derived from animaland vegetable glycerides that form water-soluble soaps andwater-insoluble emulsifying soaps, including sodium stearate, ammoniumstearate, aluminum stearate, and zinc undecylenate; ester carboxylicacids, such as dinonoxynol-9-citrate; salts of acyl lactylates such ascalcium stearoyl lactylate and laureth-6 citrate; ethercarboxylic acidsderived from ethyoxylated alcohols or phenols having varying lengths ofpolyoxyethylene chains, such as nonoxynol-8 carboxylic acid, and sodiumtrideceth-13 carboxylate; mono- and di-esters of phosphoric acid andtheir salts, such as phospholipids, dilaureth-4-phosphate, DEA-oleth-10phosphate and triethanolamine lauryl phosphate; salts ofacylisethionate, such as sodium cocoyl isethionate; alkylarylbenzenesulfonates, such as alpha-olefin sulfonates (AOS) and alkali metal,alkaline earth metal, and alkanolamine salts thereof, and sodiumdodecylbenzene sulfonate; alkyl sulfonates, such as sodium C₁₂ to C₁₄olefin sulfonate, sodium C₁₄ to C₁₆ olefin sulfonate, sodiumcocomonoglyceride sulfonate, sodium C₁₂ to C₁₅ pareth-15 sulfonate, andsodium lauryl sulfoacetate; sulfosuccinates, such as mono- and di-estersof sulfosuccinic acid, salts thereof and alkoxylated alkyl andalkylamido derivatives thereof, such as di-C₄ to C₁₀ alkyl sodiumsulfosuccinate, disodium laureth sulfosuccinate, disodium oleamidoMEA-sulfosuccinate, and disodium C₁₂ to C₁₅ pareth sulfosuccinate; alkylether sulfates, such as sodium and ammonium lauryl ether sulfate (havingabout 1 to about 12 moles ethylene oxide), e.g., sodium laureth sulfate;alkyl sulfates, such as sodium, ammonium and triethanolamine salts ofC₁₂ to C₁₈ alkylsulfates, sodium C₁₂ to C₁₄ olefin sulfates, sodiumlaureth-6 carboxylate, sodium C₁₂ to C₁₈ pareth sulfate, and the like.

Cationic surfactants can have a hydrophobe that carries a positivecharge or that is uncharged at pH values close to neutrality or lower,such as alkylamines, alkyl imidazolines, ethoxylated amines, andquaternary ammonium compounds. Cationic surfactants used in cosmeticsare preferably N-derivatives and the neutralizing anion may be inorganicor organic. Among the cationic surfactant materials useful herein arequaternary ammonium compounds corresponding to the general formula:(R¹⁴R¹⁵R¹⁶R¹⁷N⁺)E⁻, wherein each of R¹⁴, R¹⁵, R¹⁶, and R¹⁷ areindependently selected from an aliphatic group having from 1 to about 30carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido,hydroxyalkyl, aryl or alkylaryl group having 1 to about 22 carbon atomsin the alkyl chain; and E⁻ is a salt-forming anion such as thoseselected from halogen, (e.g. chloride, bromide), acetate, citrate,lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate. Thealiphatic groups can contain, in addition to carbon and hydrogen atoms,ether linkages, ester linkages, and other groups such as amino groups.The longer chain aliphatic groups, e.g., those of about 12 carbons, orhigher, can be saturated or unsaturated.

Alkylamines can be salts of primary, secondary and tertiary fatty C₁₂ toC₂₂ alkylamines, substituted or unsubstituted, and substances sometimesreferred to as “amidoamines”. Non-limiting examples of alkyl amines andsalts thereof include dimethyl cocamine, dimethyl palmitamine,dioctylamine, dimethyl stearamine, dimethyl soyamine, soyamine, myristylamine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine,ethoxylated stearylamine, dihydroxy ethyl stearylamine,arachidylbehenylamine, dimethyl lauramine, stearylamine hydrochloride,soyamine chloride, stearylamine formate, N-tallowpropane diaminedichloride, and amodimethicone (INCI name for a silicone polymer andblocked with amino functional groups, such as aminoethylaminopropylsiloxane). Non-limiting examples of amidoamines and salts thereofinclude stearamido propyl dimethyl amine, stearamidopropyl dimethylaminecitrate, palmitamidopropyl diethylamine, and cocamidopropyldimethylamine lactate. Other cationic surfactants includedistearyldimonium chloride, dicetyldimonium chloride, guarhydroxypropyltrimonium chloride, and the like. At low pH, amine oxidesmay protonate and behave similarly to N-alkyl amines.

Non-limiting examples of alkyl imidazolines include alkyl hydroxyethylimidazoline, such as stearyl hydroxyethyl imidazoline, coco hydroxyethylimidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.Non-limiting examples of ethyoxylated amines include PEG-cocopolyamine,PEG-15 tallow amine, quaternium-52, and the like.

Quaternary ammonium compounds are monomeric or polymeric materialscontaining at least one nitrogen atom that is linked covalently to fouralkyl and/or aryl substituents, and the nitrogen atom remains positivelycharged regardless of the environmental pH. Quaternary ammoniumcompounds comprise a large number of substances that are usedextensively as surfactants, conditioners, antistatic agents, andantimicrobial agents and include, alkylbenzyldimethyl ammonium salts,alkyl betaines, heterocyclic ammonium salts, and tetraalkylammoniumsalts. Long-chain (fatty) alkylbenzyldimethyl ammonium salts arepreferred as conditioners, as antistatic agents, and as fabricsofteners, discussed in more detail below. Other quaternary ammoniumcompounds include quaternary ammonium silicones. An extensive listing ofquaternary ammonium compounds suitable for use herein and theirfunctions appears in the INCI Dictionary, generally, and in Vol. 2,Section 4 of the Seventh Edition, both of which are incorporated hereinby reference.

Non-limiting examples of alkylbenzyldimethylammonium salts includestearalkonium chloride, benzalkonium chloride, quaternium-63,olealkonium chloride, didecyldimonium chloride, and the like. Alkylbetaine compounds include alkylamidopropyl betaine, alkylamidopropylhydroxysultaine, and sodium alkylamido propyl hydroxyphostaine.Non-limiting examples of alkyl betaine compounds include oleyl betaine,coco-betaine, cocamidopropylbetaine, coco-hydroxy sultaine,coco/oleamidopropyl betaine, coco-sultaine, cocoamidopropylhydroxysultaine, and sodium lauramidopropyl hydroxyphostaine. Heterocyclicammonium salts include alkylethyl morpholinium ethosulfate, isostearylethylimidonium ethosulfate, and alkylpyridinium chlorides, and aregenerally used as emulsifying agents. Non-limiting examples ofheterocyclic ammonium salts include cetylpyridinium chloride,isostearylethylimidonium ethosulfate, and the like. Non-limitingexamples of tetraalkylammonium salts include cocamidopropylethyldimonium ethosulfate, hydroxyethyl cetyldimonium chloride,quaternium-18, and cocodimonium hyroxypropyl hydrolyzed protein, such ashair keratin, and the like.

Suitable amphoteric or zwitterionic surfactants for use in the presentcompositions include those broadly described as derivatives of aliphaticquaternary ammonium, phosphonium, and sulfonium compounds, wherein whichthe aliphatic radicals can be straight chain or branched, and whereinone of the aliphatic substituents contains about 8 to about 30 carbonatoms and another substituent contains an anionic water-solubilizinggroup, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, andthe like. Classes of zwitterionics include alkylamino sulfonates, alkylbetaines and alkylamido betaines, such as stearamidopropyldimethylamine,diethylaminoethylstearamide, dimethylstearamine, dimethylsoyamine,soyamine, myristylamine, tridecylamine, ethylstearylamine,N-tallowpropane diamine, ethoxylated (5 moles ethylene oxide)stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, andthe like. Some suitable betaine surfactants include but are not limitedto alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines,alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamidopropyl hydroxysultaines, acyl taurates, and acyl glutamates,wherein the alkyl and acyl groups have from 8 to 18 carbon atoms.Non-limiting examples of preferred amphoteric surfactants includecocamidopropyl betaine, sodium cocoamphoacetate, disodiumcocoamphodiacetate, cocamidopropyl hydroxysultaine, and sodiumcocoamphopropionate, which are particularly suitable as mild-typecleansers for skin and hair.

Nonionic surfactants are generally uncharged amphiphiles and usually arealkoxylated to varying degrees. Classes of nonionic surfactants includealcohols, alkanolamides, amine oxides, alkyl glucosides, esters, andethers. Nonionic alcohols are usually hydroxy derivatives of long-chainC₈ to C₁₈ alkane hydrocarbons, such as cetearyl alcohol, hydrogenatedtallow alcohol, lanolin alcohols, alkanolamides, and the like.Alkanolamides contain at least one alkoxyl or one polyoxyethylenegrouping and include alkanol-derived amides, such as acylamide DEA,N-alkyl pyrrolidone, palmamide MEA, peanutamide MIPA, and the like andethoxylated amides, such as PEG-50 tallow amide. Amine oxides includealkylamine oxides, such as lauramine oxide; and acylamidopropylmorpholine oxides, such as cocamidopropylamine oxide; and the like. Thealkyl glucosides include linear and branched C₄ to C₂₄ alkyl glucosides,such as for example nonyl, decyl, dodecyl and lauryl glycoside. Estersinclude ethoxylated carboxylic acids, such as PEG-8 dilaurate, PEG-8laurate, and the like; ethoxylated glycerides, such as PEG-4 castor oil,PEG-120 glyceryl stearate, triolein PEG-6 esters, and the like; glycolesters and derivatives thereof, such as glycol stearate SE, propyleneglycol ricinoleate, and the like; monoglycerides, such as glycerylmyristate, glyceryl palmitate lactate, and the like; polyglycerylesters, such as polyglyceryl-6-distearate, polyglyceryl-4 oleyl ether,and the like, polyhydric alcohol esters and ethers, such as methylgluceth-20 sesquistearate, sucrose distearate; and the like;sorbitan/sorbitol esters, such as polysorbate-20, polysorbate-60,sorbitan sequiisostearate, and the like; and triesters of phosphoricacid, such as trideceth-3 phosphate, trioleth-8 phosphate, and the like.Exemplary ethers include ethoxylated alcohols, such as, Ceteareth-10,Ceteth-10, Ceteth-20, Isoceteth-20, Steareth-10, Steareth-16,Steareth-20, Steareth-25, Oleth-2, Oleth-10, Oleth-20, nonoxynol-9, andthe like; ethoxylated lanolin, such as PEG-20 lanolin, PPG-12-PEG-65lanolin oil, and the like; ethoxylated polysiloxanes, such asdimethicone copolyol, and the like; propoxylated POE ethers, such asmeroxapol 314, poloxamer 122, PPG-5-ceteth-20, and the like; and alkylpolyglycosides, such as lauryl glucose, and the like.

Non-limiting examples of nonionic surfactants include linear or branchedalcohol ethoxylates, C₈ to C₁₂ alkylphenol alkoxylates, such asoctylphenol ethoxylates, polyoxyethylene polyoxypropylene blockcopolymers, and the like; C₈ to C₂₂ fatty acid esters of polyoxyethyleneglycol mono- and di-glycerides; sorbitan esters and ethoxylated sorbitanesters; C₈ to C₂₂ fatty acid glycol esters; block copolymers of ethyleneoxide and propylene oxide; and the like. Non-limiting examples ofsurfactant boosters or hydrotropes include alkanolamides, such asacetamide MEA, monoethanolamide, diethanolamide, lauramide DEA, cocamideMEA, cocamide DEA, isopropanolamide, and the like; amine oxides, such ashydrogenated tallowamine oxide; short chain alkyl aryl sulfonates, suchas sodium toluene sulfonate; sulfosuccinates, such as disodium stearylsulfosuccinate; and the like.

Any known conditioning agent is useful in the hair fixative compositionsof this invention. Conditioning agents function to improve the sensoryand physical attributes of the hair and scalp, e.g., improvement insoftness, feel, and body (fullness), promotion of detangling under wetand dry combing conditions, reduction or elimination of static chargefrom the hair and/or skin, etc. In one aspect of the invention, theconditioning agents can be selected from synthetic oils, natural oils(e.g., vegetable, plant and animal oils), mineral oils, natural andsynthetic waxes, cationic polymers, cationic surfactants, monomeric andpolymeric quaternized ammonium salt compounds, silicones (e.g., siliconeoils, resins and gums), proteins, hydrolyzed proteins, fatty acids,fatty amines; and mixtures thereof.

The synthetic oils include polyolefins, e.g., poly-α-olefins such aspolybutenes, polyisobutenes and polydecenes. The polyolefins can behydrogenated. Fluorinated or perfluorinated oils are also contemplatedwithin the scope of the present invention. Fluorinated oils includeperfluoropolyethers described in EP-A-486135 and the fluorohydrocarboncompounds described in WO 93/11103. The fluoridated oils may also befluorocarbons such as fluoramines, e.g., perfluorotributylamine,fluoridated hydrocarbons, such as perfluorodecahydronaphthalene,fluoroesters, and fluoroethers.

Suitable natural oils include but are not limited to peanut, sesame,avocado, coconut, cocoa butter, almond, safflower, corn, cotton seed,sesame seed, walnut oil, castor, olive, jojoba, palm, palm kernel,soybean, wheat germ, linseed, sunflower seed; eucalyptus, lavender,vetiver, litsea, cubeba, lemon, sandalwood, rosemary, chamomile, savory,nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, and bergamotoils, fish oils, glycerol tricaprocaprylate; and mixtures thereof.

Suitable natural and synthetic waxes include but are not limited tocarnauba wax, candelila wax, alfa wax, paraffin wax, ozokerite wax,olive wax, rice wax, hydrogenated jojoba wax, bees wax, modified beeswax, e.g., cerabellina wax, marine waxes, polyolefin waxes, e.g.,polyethylene wax; and mixtures thereof.

In one aspect, suitable cationic polymers include but are not limited tohomopolymers and copolymers derived from free radically polymerizableacrylic or methacrylic ester or amide monomers. The copolymers cancontain one or more units derived from acrylamides, methacrylamides,diacetone acrylamides, acrylic or methacrylic acids or their esters,vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinylesters. Exemplary polymers include copolymers of acrylamide and dimethylamino ethyl methacrylate quaternized with dimethyl sulfate or with analkyl halide; copolymers of acrylamide and methacryloyl oxyethyltrimethyl ammonium chloride; the copolymer of acrylamide andmethacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers ofvinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionallyquaternized, such as the products sold under the name GAFQUAT™ byInternational Specialty Products; the dimethyl amino ethylmethacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such asthe product sold under the name GAFFIX™ VC 713 by InternationalSpecialty Products; the vinyl pyrrolidone/methacrylamidopropyldimethylamine copolymer, marketed under the name STYLEZE™ CC 10 byInternational Specialty Products; and the vinyl pyrrolidone/quaternizeddimethyl amino propyl methacrylamide copolymers such as the product soldunder the name GAFQUAT™ HS 100 by International Specialty Products.

In a still further aspect suitable cationic polymer conditioners areselected from the quaternary polymers of vinyl pyrrolidone and vinylimidazole such as the products sold under the trade name Luviquat®(product designation FC 905, FC 550, and FC 370) by BASF.

Other non-limiting examples of quaternary ammonium compounds useful ascationic conditioners in the present invention include acetamidopropyltrimonium chloride, behenamidopropyl dimethylamine, behenamidopropylethyldimonium ethosulfate, behentrimonium chloride, cetethylmorpholinium ethosulfate, cetrimonium chloride, cocoamidopropylethyldimonium ethosulfate, dicetyldimonium chloride, dimethiconehydroxypropyl trimonium chloride, hydroxyethyl behenamidopropyl dimoniumchloride, quaternium-26, quaternium-27, quaternium-53, quaternium-63,quaternium-70, quaternium-72, quaternium-76 hydrolyzed collagen, PPG-9diethylmonium chloride, PPG-25 diethylmonium chloride, PPG-40diethylmonium chloride, stearalkonium chloride, stearamidopropyl ethyldimonium ethosulfate, steardimonium hydroxypropyl hydrolyzed wheatprotein, steardimonium hydroxypropyl hydrolyzed collagen, wheatgermamidopropalkonium chloride, wheat germamidopropyl ethyldimoniumethosulfate, polymers and copolymers of dimethyl diallyl ammoniumchloride, such as Polyquaternium-4, Polyquaternium-6, Polyquaternium-7,Polyquaternium-10, Polyquaternium-11, Polyquarternium-16,Polyquaternium-22, Polyquaternium-24, Polyquaternium-28,Polyquaternium-29, Polyquaternium-32, Polyquaternium-33,Polyquaternium-35, Polyquaternium-37, Polyquaternium-39,Polyquaternium-44, Polyquaternium-46, Polyquaternium-47,Polyquaternium-52, Polyquaternium-53, Polyquarternium-55,Polyquaternium-59, Polyquaternium-61, Polyquaternium-64,Polyquaternium-65, Polyquaternium-67, Polyquaternium-69,Polyquaternium-70, Polyquaternium-71, Polyquaternium-72,Polyquaternium-73, Polyquaternium-74, Polyquaternium-76,Polyquaternium-77, Polyquaternium-78, Polyquaternium-79,Polyquaternium-80, Polyquaternium-81, Polyquaternium-82,Polyquaternium-84, Polyquaternium-85, Polyquaternium-87,PEG-2-cocomonium chloride, and mixtures thereof.

Other cationic polymer conditioners that can be used in the fixativecompositions of the invention include polyalkyleneimines such aspolyethyleneimines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrins,quaternary polyurethanes, and quaternary derivatives of chitin.

Exemplary cationic surfactants include the cationic surfactantsdisclosed hereinabove as well as salts of a primary, secondary, ortertiary fatty amine, optionally polyoxyalkylenated; a quaternaryammonium salt derivative of imidazoline, or an amine oxide. Suitableexamples include mono-, di-, or tri-alkyl quaternary ammonium compoundswith a counterion such as a chloride, methosulfate, tosylate, including,but not limited to, cetrimonium chloride, dicetyidimonium chloride,behentrimonium methosulfate, and the like.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones may be presentin the form of fluids, oils, waxes, resins, gums, and mixtures thereof.They can be volatile or non-volatile and soluble or insoluble in thefixative composition. The silicones can be selected from polyalkylsiloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes, polyorganosiloxanes modified by organofunctional groups, and mixtures thereof. Thesilicones suitable for use according to the invention include thesilicone containing polymers and copolymers described in the emulsifierand emollient disclosure hereinabove.

Suitable polyalkyl siloxanes include polydimethyl siloxanes withterminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C₁-C₂₀) siloxanes.

Suitable polyalkyl aryl siloxanes include polydimethyl methyl phenylsiloxanes and polydimethyl diphenyl siloxanes, linear or branched.

The silicone gums suitable for use herein include polydiorganosiloxanes.In one aspect the silicone gums have a number-average molecular weightbetween 200,000 and 1,000,000 Daltons. Examples include polymethylsiloxane, polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxaneand polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane.

Suitable silicone resins include silicones with a dimethyl/trimethylsiloxane structure and resins of the trimethyl siloxysilicate type.

The organo-modified silicones suitable for use in the invention includesilicones containing one or more organofunctional groups attached bymeans of a hydrocarbon radical and grafted siliconated polymers.Exemplary organo-modified silicones are amino functional silicones.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havingquaternary ammonium moieties on the polypeptide chain, including atleast one C₁-C₁₈ alkyl moiety. Hydrolyzed proteins include Croquat™ L,in which the quaternary ammonium groups include a C₁₋₂ alkyl group,Croquat™ M, in which the quaternary ammonium groups include C₁₀-C₁₈alkyl groups, Croquat™ S in which the quaternary ammonium groups includea C₁₋₈ alkyl group and Crotein™ Q in which the quaternary ammoniumgroups include at least one C₁-C₁₈ alkyl group. These products are soldby Croda International. Quaternized vegetable proteins such as wheat,corn, or soy proteins such as cocodimonium, hydrolyzed wheat protein,laurdimonium hydrolyzed wheat protein and steardimonium hydrolyzed wheatprotein are also useful as conditioning agents.

Suitable fatty acids that can be used as conditioning agents are thosepreviously described as emulsifiers, including C₁₂-C₂₂ fatty acids.Exemplary fatty acid conditioners include but are not limited tomyristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,isostearic acid, and behenic acid.

Suitable fatty amines known to be useful as a conditioning agent; e.g.dodecyl, cetyl or stearyl amines, such as stearamidopropyl dimethylamineare also useful in the fixative compositions of the invention.

The conditioning agent(s) can be present in an amount of 0.001 wt. % to20 wt. % in one aspect, from 0.01 wt. % to 10 wt. % in another aspect,and from 0.1 wt. % to 3 wt. % based on the total weight of the fixativecomposition.

In addition to the one or more cosmetically acceptable adjuvants andadditives described hereinabove, the fixative composition of the presentinvention can contain one or more additional cosmetically acceptableadjuvants and/or additives chosen from protecting and therapeuticagents, such as UV filters, antiradical agents, antioxidants, hair-lossagents, vitamins and pro-vitamins, proteinaceous materials andderivatives thereof; hair colorants, such as pigments and dyes for thetemporary, semi-permanent, or permanent coloring of the hair; hairbleaching agents; hair highlighting agents; polymer film modifyingagents, such as plasticizers, humectants, tackifiers, detackifiers,wetting agents, and the like; product finishing agents, such aschelating agents, sequestrants, buffers, opacifiers, pearlizing agents,and stabilizers; aliphatic monoalcohols, such as methyl alcohol, ethylalcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutylalcohol, t-butyl alcohol, and amyl alcohol (all isomers); polyols suchas glycols and glycerol; botanical extracts; oxidizing agents; reducingagents; lubricants; electrolytes; hair sheen enhancers; preservatives;fragrances; solubilizers; chemical hair waving or straightening agents;and detangling/wet combing agents. These adjuvants and additives can bepresent in the composition in amounts that range from 0 to 20 wt. % inrelation to the total weight of the fixative composition. The preciseamount of each adjuvant and additive to employ in a desired compositioncan be easily determined by one of ordinary skill in the field accordingto the nature and function of the ingredient. Those skilled in the hairsetting art recognize that some ingredients described herein aremultifunctional and, hence, can serve more than one purpose in theformulation, as long as the purpose and properties of the hair settingcomposition performs its intended function. An extensive listing ofcosmetic ingredients and their functions appears in the INCI Dictionary,generally, and in Vol. 2, Section 4 of the Seventh Edition, both ofwhich are incorporated herein by reference.

While overlapping weight ranges for the various ingredients, adjuvantsand additives contained in the fixative compositions of the inventionhave been disclosed for selected embodiments and aspects of theinvention, it should be readily apparent that the specific amount ofeach component in the fixative composition is selected from itsdisclosed range such that the amount of each component is adjusted sothat the sum of all components in the composition will total 100 weightpercent. The amounts of each component employed in the fixativecomposition will vary with the compatibility, purpose, and character ofthe desired component and can be readily determined by one skilled inthe formulation arts and from the literature.

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. These examples are presentedsolely for the purpose of illustration, and are not to be construed aslimitations of the present invention since many variations thereof arepossible without departing from the spirit and scope thereof. Unlessotherwise specified, weight percents (wt. %) are given in wt. % based onthe weight of the total composition.

Methods Description

High Humidity Curl Retention (HHCR) Test

The resistance of a polymer fixative composition to high humidity (about90% Relative Humidity (RH)) is measured by its ability to hold a curlset on hair after absorption of water from the applied composition andfrom the surrounding atmosphere employing the well known techniquecommonly referred to as high humidity curl retention (HHCR).Descriptions of the HHCR methodology are readily found in the cosmeticliterature (see, for example, Ch. 30, Harry's Cosmeticology, 8th Ed., M.J. Rieger, Ph.D. (ed.), pp. 666-667, Chemical Publishing Co., Inc., NewYork, N.Y., 2000, and Diaz et al., J. Soc. Cosmet. Chem., 34, pp.205-212, July 1983, the relevant disclosures of each are incorporatedherein by reference.

Tresses of commercially blended untreated (virgin) human hair areprepared employing natural brown or black color European and/or Orientalhair supplied by International Hair Importers and Products Inc., NewYork. Each hair tress (about 2.5 grams weight) is about 7.5 inches inlength and is crimped (by the root portion) within a metal clampequipped with a wire hanger loop. Prior to use, each tress is washedwith a dilute aqueous solution of sodium lauryl sulfate (10% SLS)followed by thorough rinsing with deionized water at ambient roomtemperature. The tresses are dried by towel blotting. The initialextended length of the hair tress (L_(e)) is measured and recorded.Varying amounts of polymer fixative composition to be evaluated areapplied to each hair tress. The polymer fixative composition to beevaluated is applied to the hair tress and distributed uniformly fromthe root portion of the hair to tip portion. The treated hair tress iswrapped around a hair curler having an outer diameter of about 3 cm anddried for 12 hours at ambient room temperature of about 21 to 23° C.After drying, the curler is carefully removed, leaving the hair tressstyled into a single curl, the initial length of the hair curl (L_(i))is measured and recorded. The curled hair tress is vertically hung in ahumidity chamber set at a temperature of about 26° C. and a relativehumidity level of 90%.

High humidity curl retention is determined by measuring the length ofthe hair curl as the curl relaxes. Measurements are taken at selectedintervals of time (L_(t)) over a 24 hour continuum of exposure to highhumidity. The following equation is used to calculate percent curlretention, relative to the initial curl length (L_(i)) and length of thefully extended hair, before curling (L_(e)):% Curl Retention=L _(e) −L _(t) /L _(e) −L _(i)×100

The change in curl length (droop, helix formation) is periodicallymeasured at selected intervals and is monitored over a period of 24hours. An initial measurement is taken at time zero, followed bymeasurements at 0.25 hour intervals for the first hour of exposure,followed by measurements taken at 0.5 hour intervals for the second hourof exposure, followed by measurements taken at 1.0 hour intervals forthe remaining 22 hours of exposure.

A curl retention of about 70% or more for a minimum period of about 0.75hours at about 90% RH is a conventional benchmark for good high humidityresistance, and an HHCR greater than 70% after a period of at leastabout 3 hours is deemed very good to excellent.

High Humidity Spiral Curl Retention Test (HHSCR)

While the humidity resistance of a fixative composition can be evaluatedby the HHCR test described above. The HHCR test is performed usingregular salon roller type curlers, where the hair overlaps onto itselfas it is rolled, which protects the fibers inside the curl from the testenvironment. The curl retention test can be rendered more stringent byusing of spiral curlers. With this modification, hair is rolled into aspiral groove down the length of the curler rod without overlap. Thus,for a spiral curl, the entire length of the hair is fully exposed to theenvironment.

The same materials, methods, and evaluation techniques outlined for thepreviously described HHCR test are employed for the HHSCR test exceptthat the hair tress weighs 0.5 g, is 6.5 inches long and is wrappedaround a spiral perm rod (Cyber Sprials™ large spiral curling rods, 8 mminner diameter, 13.5 mm outer diameter, 162 mm length, American DiscountBeauty Supply, 269 South Beverly Drive # 250, Beverly Hills, Calif.).The results are reported as percent curl retention calculated by thecurl retention equation set forth above.

A curl retention of about 70% or more for a minimum period of about 0.75hours at about 90% RH is a conventional benchmark for good high humidityresistance, and an HHCR greater than 70% after a period of at leastabout 3 hours is deemed very good to excellent.

Mechanical Stiffness Test Method

A TA XTPlus Texture Analyser (Stable Micro Systems, Surrey, UK) fittedwith a rectangular loading nose (3 mm thick×70 mm wide×99 mm high) and a3-point bending rig is employed to evaluate the mechanical stiffness ofa fixative treated hair tress. The Texture Analyser is interfaced with apersonal computer loaded with Texture Exponent 32 data acquisitionsoftware that collects and analysis the data inputted from theinstrument. The bending rig consists of two parallel support legs thatare spaced apart by approximately 25.4 mm. The treated hair swatch testsample is centered across the span of the support legs and the loadingnose which is centered above and between the support legs is pressedthrough the sample at a rate of 40 mm/s for a distance of 20 mm. Dataacquisition starts when the loading nose contacts the sample. The dataacquisition software calculates and records the amount of force(Newtons) it takes to deflect the sample through a distance of 20 mm.The results are reported as Peak Force (N) and Work (N·mm).

Hair swatches (6.5″ long, 2.5 g in weight) consisting of virgin naturalhuman hair are bound with a flat (sewn and waxed) binding so that thetress has a uniform rectangular cross section along its whole length.The tresses are washed with a stripping shampoo containing 10 wt. %ammonium lauryl sulfate and rinsed with deionized water. A designatedamount of experimental fixative is evenly applied to the damp hairswatches. A first set of swatches are laid flat on Teflon® foil to dryat 23° C. and 50% relative humidity in a controlled laboratoryenvironment for 16 hours and tested A second set of swatches issimilarly prepped and subsequently placed in a humidity chamber (EspecLHU-113) set at 23° C. and 90% relative humidity for 16 hours andsubsequently tested for mechanical stiffness.

Molecular Weight Determination

The molecular weight of the cationic Cassia galactomannan polymer isdetermined by a low angle light scattering detector (Triple DetectorArray, model no. 302-040) coupled with two Visco GEL C-MBHMW-3078columns using a sample concentration of 0.6 mg/ml in a 0.05 M ammoniumacetate/10% methanol solvent (at a pH of 4.0), an injection volume of100 μL, a column temperature of 30° C., and a flow rate of 0.9 mL/min.

Viscosity

Brookfield rotating spindle method: The viscosity of each polymercontaining composition is measured as mPa·s, employing a Brookfieldrotating spindle viscometer, Model RVT (Brookfield EngineeringLaboratories, Inc.), at about 20 revolutions per minute (rpm), atambient room temperature of about 20 to 25° C. (hereafter referred to asviscosity). Appropriate spindle sizes are set forth in the examples.

Yield Value

Yield Value, also referred to as Yield Stress, is defined as the initialresistance to flow under stress. It is measured by the Brookfield YieldValue (BYV) Extrapolation Method using a Brookfield viscometer (ModelRVT). The Brookfield viscometer is used to measure the torque necessaryto rotate a spindle through a liquid sample at speeds of 0.5 to 100 rpm.Multiplying the torque reading by the appropriate constant for thespindle and speed gives the apparent viscosity. Yield Value is anextrapolation of measured values to a shear rate of zero. The BYV iscalculated by the following equation:BYV,dyn/cm²=(η_(α1)−η_(α2))/100where η_(α1) and η_(α2)=apparent viscosities obtained at two differentspindle speeds (0.5 rpm and 1.0 rpm, respectively). These techniques andthe usefulness of the Yield Value measurement are explained in TechnicalData Sheet Number 244 (Revision: 5/98) from Noveon Consumer Specialtiesof Lubrizol Advanced Materials, Inc., herein incorporated by reference.Low yield values (<50 dyns/cm²) are indicative of smooth andNewtonian-like flow properties.

EXAMPLE 1

This example describes the preparation of cationic Cassia (Cassiahydroxypropyltrimethyl ammonium chloride). To a reaction vessel 160 g ofCassia gum (containing about 10% moisture) is mixed in a solution of 921g of 44% isopropanol in water. To this mixture 4.5 g of potassiumhydroxide is added and the mixture is heated at 40° C. for 30 minutesunder nitrogen until a slurry is formed. Subsequently, 92.8 g of2,3-epoxypropyltrimethyl ammonium chloride (Quab 151 from SKW QuabChemicals Inc, 70%) is added to the slurry. The reaction slurry isheated to 70° C. and is kept at this temperature for 3 hours.

After cooling to 50° C., the slurry is diluted with 380 g of 99%isopropanol and neutralized to a pH of about 7.0 with a solution ofacetic acid (50 wt. % solution in deionized water). The Cassiahydroxypropyltrimethyl ammonium chloride product is filtered, washedonce with 380 g of isopropanol (99 wt. %), air dried overnight and ovendried at 100° C. for 4 hours to produce 179.3 of cationic Cassia. Thefinal product has a nitrogen content of 2.18 wt. % calculated on a dryweight basis of the polymer (dry wt. basis) and a charge density of 1.56meq/g. The charge density of cationically functionalized Cassia can bechanged by varying the stoichiometric amount of cationicfunctionalization agent employed in the functionalization reaction. Thequaternary nitrogen content (and thus the cationic charge density) ofcationic Cassia is increased or decreased by increasing or decreasingthe stoichiometric amount of quaternizing agent relative to the hydroxylcontent present on the Cassia backbone.

EXAMPLE 2

Aqueous dispersions in deionized water containing 2 wt. % of thecationic Cassia and cationic guar samples set forth in Table 1 below areevaluated for mechanical stiffness properties as described in theMechanical Stiffness Test Method above. Asian (Chinese) type hairswatches are prepared and treated (0.8 g of fixative composition/swatch)and evaluated for mechanical stiffness after exposure to 50% and 90%relative humidity conditions. Five replicates of each test sample areprepared and tested. The average peak force for the 5 replicates arecalculated and recorded in Table 1.

TABLE 1 Cationic Charge Relative Density Humidity Work Peak Force Sample(meq/g). (%). (N · mm) (N) Cationic Cassia 1.8 50 80.4 12.2 CationicCassia 3 50 48.8 7.6 Cationic Guar* 1.76 50 38.2 7.0 Cationic Guar* 2.950 31.8 5.4 Cationic Cassia 1.8 90 37.6 5.9 Cationic Cassia 3 90 60.79.0 Cationic Guar* 1.76 90 28.8 4.2 Cationic Guar* 2.9 90 31.1 4.7*Prepared in a manner similar to Example 1

At equivalent charge densities, cationic Cassia polymers demonstratehigher stiffness (higher peak force and Work) than cationic guar, bothat 50% and 90% relative humidity environment on Chinese hair swatches.

EXAMPLE 3

Two separate fixative gel compositions (A and B) containing 2 wt. % ofthe cationic Cassia polymers of the invention are formulated incombination with 1 wt. % (total polymer actives) of an acid swellableassociative rheology modifier (Carbopol® Aqua CC, Lubrizol AdvancedMaterials, Inc.; INCI Name: Polyacrylates-1 Crosspolymer). The cationicCassia polymers are prepared by the method set forth in Example 1 exceptthat the cationic Cassia contained in composition (A) contains 4.2 wt. %nitrogen (dry wt. basis) and a charge density of 3.0 meq/g, and thecationic Cassia contained in composition (B) contains 2.3 wt. % nitrogen(dry wt. basis) and a charge density of 1.6 meq/g. An identicallyformulated gel fixative composition utilizing a commercially availablecationic guar, Jaguar™ C13S (Rhodia, Inc.), containing 1.5 wt. %nitrogen (dry wt. basis) and a charge density of 1.0 meq/g is preparedfor comparative HHSCR test evaluations.

The tresses for this test are comprised of European brown hair, weighing0.5 g, 6.5 inches long and 0.5 inches wide. To each tress 0.1 g of thepolymer gel is uniformly applied and the treated tresses are tested asset forth in the HHSCR Test methodology disclosed above. Ten replicatesof each of the fixative treated tresses were evaluated and the averagepercent retention values are plotted in FIG. 1.

The cationic Cassia fixative gels (in combination with Polyacrylates-1Crosspolymer) display superior spiral curl retention properties at highhumidity compared to the commercially available cationic guar, Jaguar™C13S, independent of cationic Cassia charge density. Both cationicCassia polymers (Composition (A) charge density: 3.0 meq/g andComposition (B) charge density: 1.6 meq/g) display over 85% spiral curlretention after 24 hours at 90% relative humidity and 23° C. Incomparison, cationic guar, Jaguar™ C13S (charge density: 1 meq/g)displays 60% spiral curl retention after 24 hours at 90% relativehumidity and 23° C.

EXAMPLE 4

The fixative gel compositions of Example 3 are evaluated for mechanicalstiffness properties as described in the Mechanical Stiffness TestMethod above. European brown hair swatches are prepared and treated (0.8g of fixative composition/swatch) and evaluated for mechanical stiffnessafter exposure to 47% and 90% relative humidity conditions. Fivereplicates of each test sample are prepared and tested. The average peakforce for the 5 replicates are calculated and recorded in Table 2.

TABLE 2 Relative Peak Humidity Work Force Sample (%) (N · mm) (N) 2 wt %Composition A (3 meq/g) 47 61.8 9.9 2 wt % Composition B (1.6 meq/g) 4752.9 9.4 2 wt % Jaguar ™ C13S (1 meq/g) 47 41.5 6.8 2 wt % Composition A(3 meq/g) 90 46.0 6.5 2 wt % Composition B (1.6 meq/g) 90 50.4 6.6 2 wt% Jaguar ™ C13S (1.0 meq/g) 90 38.2 5.5

Both cationic Cassia fixative gel compositions display significantlyhigher stiffness (Peak Force and Work) than cationic guar at 47%relative humidity. The same trend but with less dramatic differences isobserved at 90% relative humidity.

EXAMPLE 5

A fixative gel formulated with 2 wt. % of the cationic Cassia set forthin composition A of Example 3 (charge density: 3.0 meq/g) and 1 wt. %guar gum (Novegum G888, Lubrizol Advanced Materials, Inc.) is evaluatedfor curl retention as described in the HHCR Test. European brown hairswatches and hair tresses are utilized in the respective evaluations.Nine replicates of each treated hair swatch and hair tress areevaluated. The cationic Cassia polymer in combination with guar gumdisplay excellent high humidity curl retention over 95.5% curl retentionafter 24 hours at 90% relative humidity and 23° C. The averages of theresults are plotted in FIG. 2.

EXAMPLE 6

Aqueous fixative gels are made utilizing the cationic Cassia describedin composition A of Example 3 (charge density: 3.0 meq/g) and guar gum(Novegum™ G888). The amounts of formulation components, viscosity andyield value data of the various gels are reported in Table 3.

TABLE 3 Brookfield Viscosity at 20 rpm Spindle Yield Value FixativeSample (mPa · s) Size (dyn/cm²) 1 wt % Cationic Cassia 324 1 0 (3 meq/g)in deionized water 2 wt % Cationic Cassia 3,180 3 0 (3 meq/g) indeionized water 1 wt % guar (Novegum ™ G888) 4,310 3 22 in deionizedwater 2 wt % guar (Novegum ™ G888) 31,100 7 620 in deionized water Blendof 1 wt % cationic Cassia 17,300 4 160 (3 meq/g) and 1 wt % guar gum(Novegum ™ G888) in deionized water Blend of 2 wt % cationic Cassia38,700 7 560 (3 meq/g) and 1 wt % guar gum (Novegum ™ G888) in deionizedwater

An unexpected synergy occurs (viscosity and yield value increase) whenblends of the cationic Cassia of the invention and guar are formulatedtogether.

EXAMPLE 7

The fixative compositions set forth in Example 6 are evaluated formechanical stiffness properties as described in the Mechanical StiffnessTest Method above. European brown hair swatches are prepared and treated(0.8 g of fixative composition/swatch) and evaluated for mechanicalstiffness after exposure to 90% relative humidity conditions. Fivereplicates of each test sample are prepared and tested. The average PeakForce and Work for the 5 replicates are calculated and recorded in Table4.

TABLE 4 Peak force Work Fixative Sample (N) (N · mm) 1 wt. % cationicCassia 9.2 46.1 (3 meq/g) in deionized water 2 wt. % cat Cassia indeionized 13.7 68.2 water 1 wt. % guar gum (Novegum ™ 4.9 33.9 G888) indeionized water 2 wt. % guar gum (Novegum ™ 4.9 33.9 G888) in deionizedwater Blend 1 wt. % cationic Cassia 14.9 81.2 (3 meq/g) and 1 wt % guargum (Novegum ™ G888) in deionized water Blend 2 wt. % cationic Cassia15.3 90.5 (3 meq/g) and 1 wt % guar gum (Novegum ™ G888) in deionizedwater

The cationic Cassia polymer fixative compositions display high stiffnessvalues. The gels made of a blend of cationic Cassia (charge density: 3meq/g) and guar gum Noveg UM G888 display even higher synergisticstiffness (higher peak force and work) at 90% relative humidity at 23°C. compared to the individual neat components. The peak force values ofthe compositions are plotted in FIG. 3. In FIG. 3, Point A representsthe 2 wt. % cationic Cassia (0 wt. % guar gum) in deionized waterformulation, Point B represents the blend of 1 wt. % cationic Cassia and1 wt % guar gum in deionized water formulation, and Point C representsthe 2 wt. % guar gum (0 wt. % cationic Cassia) in deionized waterformulation.

EXAMPLE 8

The fixative compositions set forth in Example 6 are evaluated onEuropean brown hair tresses for curl retention in the HHSCR Test at 90%relative humidity at 23° C. To each tress 0.1 g of the fixative gel isuniformly applied and the treated tresses are tested as set forth in theHHSCR Test methodology disclosed above. Ten replicates of each of thefixative treated tresses were evaluated and the average percent curlretention values set forth in Table 5.

TABLE 5 Spiral curl Spiral retention at 8 curl retention at 24 FixativeSample hours (%) hours (%) 1 wt % cationic Cassia (3 meq/g) in 85.3 85.9deionized water 2 wt % cationic Cassia in deionized 88.3 87.2 water 1 wt% Guar G888 in deionized 68.0 68.0 water 2 wt % guar G888 in deionized79.8 77.6 water Blend 1 wt % cationic Cassia 89.7 89.7 (3 meq/g) and 1wt % guar gum (Novegum ™ G888) in deionized water Blend 2 wt % cationicCassia 93.3 93.3 (3 meq/g) and 1 wt % guar gum (Novegum ™ G888) indeionized water

Both cationic Cassia dispersions (at 1 and 2 wt. %) and the gels madefrom a blend of cationic Cassia (3 meq/g) and guar gum (Novegum™ G888)display high excellent spiral curl retention after 8 and 24 hours atexposure to 90% relative humidity at 23° C.

1. A hair fixative composition comprising: a) a polygalactomannan having repeating units containing a D-mannosyl to D-galactosyl residue ratio of at least 5 to 1, said D-mannosyl and D-galactosyl residues having pendant hydroxyl groups, and wherein a portion of the hydrogen groups on the pendant hydroxy substituents on the mannosyl and galactosyl residues are substituted with a group represented by the formula: -AR¹ wherein A is a substituted or unsubstituted alkylene group containing 1 to 6 carbon atoms, and R¹ is a group independently —N(R³)₃ ⁺X⁻, —S(R³)₂ ⁺X⁻, and —P(R³)₃ ⁺X⁻; wherein R³ independently represents substituted and unsubstituted C₁ to C₂₄ alkyl, substituted and unsubstituted benzyl and substituted and unsubstituted phenyl; and X is any suitable anion that balances the charge on the onium cation; and b) guar gum; and c) polyacrylate-1 crosspolymer wherein the weight ratio of said polygalactomannan to said guar gum ranges from 1:5 to 5:1.
 2. A hair fixative composition of claim 1 wherein A is an substituted alkylene radical substituted with one or more substituents selected from C₁ to C₃ alkyl, C₁ to C₃ haloalkyl, hydroxyl, and halogen,
 3. A hair fixative composition of claim im 1 wherein X is a halide.
 4. A hair fixative composition of claim 1 wherein said polygalactomannan repeating unit is represented by the formula:

wherein R independently represents hydrogen, and -AR¹, wherein -AR¹ is defined as above, and n represents the number of repeating units in the polygalactomannan such the number average molecular weight ranges from 200,000 to 3,000,000 Daltons.
 5. A hair fixative composition of claim 4 wherein at least one C-6 hydroxyl hydrogen is substituted by the -AR¹ substituent.
 6. A hair fixative composition of claim 1 further comprising an ingredient selected from an auxiliary hydrocolloid, an auxiliary fixative, a solvent, a propellant, and mixtures thereof.
 7. A hair fixative composition of claim 6 further comprising an ingredient selected from a pH adjusting agent, emulsifier(s), emollient(s), surfactant(s), conditioning agent(s), and mixtures thereof.
 8. A hair fixative composition of claim 6 further comprising an ingredient selected from protecting agent(s), therapeutic agent(s), hair colorant(s), hair bleaching agent(s), hair highlighting agent(s), polymer film modifying agent(s), product finishing agent(s), aliphatic monoalcohol(s), polyol(s), botanical extract(s), oxidizing agent(s), reducing agent(s), lubricangs), electrolyte(s), hair sheen enhancer(s), preservative(s), fragrance(s), solubilizer(s), chemical hair waving agent(s), hair straightening agent(s), detangling agent(s), wet combing agent(s), and mixtures thereof
 9. A hair fixative composition of claim 6 wherein said auxiliary hydrocolloid is a polygalactomannan gum is selected from Cassia gum, tara gum, locust bean gum, fenugreek gum, and mixtures thereof.
 10. A hair fixative composition of claim 6 wherein said solvent is selected from an aliphatic monoalcohol(s), polyol(s), water, and mixtures thereof.
 11. A hair fixative composition of claim 7 wherein said surfactant is selected from an anionic surfactant(s), a cationic surfactant (s), a nonionic surfactant(s), an amphoteric surfactant(s), a zwitterionic surfactant(s), and mixtures thereof.
 12. A hair fixative composition of claim 7 in the form of a pumpable spray, pressurized spray, mousse, gel, spritz, and foam.
 13. A hair fixative composition of claim 1 wherein the weight ratio of said polygalactomannan to said guar gum ranges from 1:1 to 2:1.
 14. A hair fixative composition of claim 1 wherein said -AR¹ moiety is represented by the formula:

wherein R³ is selected from C₁ to C₂₄ alkyl, benzyl and phenyl, and R⁴ is chlorine or hydrogen.
 15. A hair fixative composition of claim 14 wherein said -AR¹ moiety is 2-hydroxy-3-(trimethylammonium)propyl chloride. 